Catalyst System With Three Metallocenes for Producing Broad Molecular Weight Distribution Polymers

ABSTRACT

Disclosed herein are polymerization processes for the production of olefin polymers. These polymerization processes use a catalyst system containing three metallocene components, often resulting in polymers having a reverse comonomer distribution and a broad and non-bimodal molecular weight distribution.

BACKGROUND OF THE INVENTION

Polyolefins such as high density polyethylene (HDPE) homopolymer andlinear low density polyethylene (LLDPE) copolymer can be produced usingvarious combinations of catalyst systems and polymerization processes.Chromium based and Ziegler based catalyst systems can, for example,produce polymer resins having good processability, typically due totheir broad molecular weight distribution (MWD). In contrast, polymersproduced using catalyst systems containing a single metallocene compoundgenerally have a narrow MWD and, accordingly, poor processability. BroadMWD and bimodal resins can be made from dual metallocene catalystsystems. However, some broad MWD bimodal resins can experienceprocessing issues, such as melt fracture, due to the disparity inmolecular weights of the two components of the MWD. Moreover, chromiumbased and Ziegler based catalyst systems often produce polymers in whichmore of the comonomer is present in the lower molecular weight fractionof the polymer. The presence of more comonomer in the higher molecularweight fraction of the polymer, often referred to as a reverse comonomerdistribution or a reverse short chain branching distribution (SCBD),often can improve physical properties in various end-use applications.

In view of these generalities, it would be beneficial to produce broadmolecular weight distribution polymers having a reverse comonomer orreverse SCBD. Accordingly, it is to these ends that the presentinvention is directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

The present invention generally relates to new catalyst compositions,methods for preparing catalyst compositions, methods for using thecatalyst compositions to polymerize olefins, the polymer resins producedusing such catalyst compositions, and articles produced using thesepolymer resins. In particular, aspects of the present invention aredirected to catalyst compositions employing three metallocene catalystcomponents. The first catalyst component can comprise an unbridgedzirconium or hafnium based metallocene compound and/or an unbridgedzirconium and/or hafnium based dinuclear metallocene compound; thesecond catalyst component can comprise a bridged zirconium basedmetallocene compound with a fluorenyl group, and with no aryl groups onthe bridging group; and the third catalyst component can comprise abridged zirconium or hafnium based metallocene compound with a fluorenylgroup, and an aryl group on the bridging group. Such catalystcompositions can be used to produce, for example, ethylene-basedhomopolymers and copolymers having broad molecular weight distributions.

In one aspect, a catalyst composition is disclosed which can comprisethe first metallocene catalyst component, the second metallocenecatalyst component, the third metallocene component, and an activator.Optionally, this catalyst composition can further comprise aco-catalyst.

The present invention also contemplates and encompasses olefinpolymerization processes. Such processes can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer under polymerization conditions to produce an olefin polymer.Generally, the catalyst composition employed can comprise any of thecatalyst component I metallocene compounds, any of the catalystcomponent II metallocene compounds, any of the catalyst component IIImetallocene compounds, and any of the activators and optionalco-catalysts disclosed herein. For example, organoaluminum compounds canbe utilized in the catalyst compositions and/or polymerizationprocesses.

Polymers produced from the polymerization of olefins, resulting inhomopolymers, copolymers, terpolymers, etc., can be used to producevarious articles of manufacture. A representative and non-limitingexample of an olefin polymer (e.g., an ethylene copolymer) consistentwith aspects of this invention can be characterized as having thefollowing properties: a melt index in a range from about 0.005 to about10 g/10 min, a ratio of HLMI/MI in a range from about 50 to about 500, adensity in a range from about 0.915 g/cm³ to about 0.965 g/cm³, and anon-bimodal molecular weight distribution.

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects andembodiments may be directed to various feature combinations andsub-combinations described in the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 illustrates a representative bimodal molecular weightdistribution curve.

FIG. 2 illustrates a representative bimodal molecular weightdistribution curve.

FIG. 3 illustrates a representative bimodal molecular weightdistribution curve.

FIG. 4 illustrates a representative bimodal molecular weightdistribution curve.

FIG. 5 illustrates a representative bimodal molecular weightdistribution curve.

FIG. 6 illustrates a representative non-bimodal molecular weightdistribution curve.

FIG. 7 illustrates a representative non-bimodal molecular weightdistribution curve.

FIG. 8 illustrates a representative non-bimodal molecular weightdistribution curve.

FIG. 9 illustrates a representative non-bimodal molecular weightdistribution curve.

FIG. 10 illustrates a representative non-bimodal molecular weightdistribution curve.

FIG. 11 illustrates a representative non-bimodal molecular weightdistribution curve.

FIG. 12 illustrates the definitions of D85 and D15 on a molecular weightdistribution curve.

FIG. 13 illustrates the definitions of D50 and D10 on a molecular weightdistribution curve and the short chain branch content at D50 and D10.

FIG. 14 presents a plot of the molecular weight distributions of thepolymers of Examples 1-6.

FIG. 15 presents a plot of the short chain branching distribution of thepolymer of Example 1.

FIG. 16 presents a plot of the short chain branching distribution of thepolymer of Example 2.

FIG. 17 presents a plot of the short chain branching distribution of thepolymer of Example 3.

FIG. 18 presents a plot of the short chain branching distribution of thepolymer of Example 4.

FIG. 19 presents a plot of the short chain branching distribution of thepolymers of Examples 5-6.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Regarding claim transitional terms or phrases, the transitional term“comprising”, which is synonymous with “including,” “containing,” or“characterized by,” is open-ended and does not exclude additional,unrecited elements or method steps. The transitional phrase “consistingof” excludes any element, step, or ingredient not specified in theclaim. The transitional phrase “consisting essentially of” limits thescope of a claim to the specified components or steps and those that donot materially affect the basic and novel characteristic(s) of theclaimed invention. A “consisting essentially of” claim occupies a middleground between closed claims that are written in a “consisting of”format and fully open claims that are drafted in a “comprising” format.For example, a feedstock consisting essentially of component A caninclude impurities typically present in a commercially produced orcommercially available sample of component A. When a claim includesdifferent features and/or feature classes (for example, a method step,feedstock features, and/or product features, among other possibilities),the transitional terms comprising, consisting essentially of, andconsisting of, apply only to the feature class to which it is utilizedand it is possible to have different transitional terms or phrasesutilized with different features within a claim. For example, a methodcan consist of certain steps, but utilize a catalyst system comprisingrecited components and other non-recited components. While compositionsand methods are described herein in terms of “comprising” variouscomponents or steps, the compositions and methods can also “consistessentially of” or “consist of” the various components or steps, unlessstated otherwise. For example, a catalyst composition consistent withaspects of the present invention can comprise; alternatively, canconsist essentially of; or alternatively, can consist of; (i) catalystcomponent I, (ii) catalyst component II, (iii) an activator, and (iv)optionally, a co-catalyst.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an activator-support” or “a metallocenecompound” is meant to encompass one, or mixtures or combinations of morethan one, activator-support or metallocene compound, respectively,unless otherwise specified.

Groups of elements are indicated using the numbering scheme indicated inthe version of the periodic table of elements published in Chemical andEngineering News, 63(5), 27, 1985. In some instances, a group ofelements can be indicated using a common name assigned to the group; forexample, alkali metals for Group 1 elements, alkaline earth metals forGroup 2 elements, transition metals for Group 3-12 elements, andhalogens or halides for Group 17 elements.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

A chemical “group” is described according to how that group is formallyderived from a reference or “parent” compound, for example, by thenumber of hydrogen atoms formally removed from the parent compound togenerate the group, even if that group is not literally synthesized inthis manner. These groups can be utilized as substituents or coordinatedor bonded to metal atoms. By way of example, an “alkyl group” formallycan be derived by removing one hydrogen atom from an alkane, while an“alkylene group” formally can be derived by removing two hydrogen atomsfrom an alkane. Moreover, a more general term can be used to encompass avariety of groups that formally are derived by removing any number (“oneor more”) of hydrogen atoms from a parent compound, which in thisexample can be described as an “alkane group,” and which encompasses an“alkyl group,” an “alkylene group,” and materials have three or morehydrogen atoms, as necessary for the situation, removed from the alkane.The disclosure that a substituent, ligand, or other chemical moiety canconstitute a particular “group” implies that the well-known rules ofchemical structure and bonding are followed when that group is employedas described. When describing a group as being “derived by,” “derivedfrom,” “formed by,” or “formed from,” such terms are used in a formalsense and are not intended to reflect any specific synthetic method orprocedure, unless specified otherwise or the context requires otherwise.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Unless otherwise specified, “substituted” is intended to be non-limitingand include inorganic substituents or organic substituents as understoodby one of ordinary skill in the art.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thatthe presence of one or more halogen atoms replacing an equivalent numberof hydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” isused herein in accordance with the definition specified by IUPAC: aunivalent group formed by removing a hydrogen atom from a hydrocarbon(that is, a group containing only carbon and hydrogen). Non-limitingexamples of hydrocarbyl groups include ethyl, phenyl, tolyl, propenyl,and the like. Similarly, a “hydrocarbylene group” refers to a groupformed by removing two hydrogen atoms from a hydrocarbon, either twohydrogen atoms from one carbon atom or one hydrogen atom from each oftwo different carbon atoms. Therefore, in accordance with theterminology used herein, a “hydrocarbon group” refers to a generalizedgroup formed by removing one or more hydrogen atoms (as necessary forthe particular group) from a hydrocarbon. A “hydrocarbyl group,”“hydrocarbylene group,” and “hydrocarbon group” can be aliphatic oraromatic, acyclic or cyclic, and/or linear or branched. A “hydrocarbylgroup,” “hydrocarbylene group,” and “hydrocarbon group” can includerings, ring systems, aromatic rings, and aromatic ring systems, whichcontain only carbon and hydrogen. “Hydrocarbyl groups,” “hydrocarbylenegroups,” and “hydrocarbon groups” include, by way of example, aryl,arylene, arene groups, alkyl, alkylene, alkane group, cycloalkyl,cycloalkylene, cycloalkane groups, aralkyl, aralkylene, and aralkanegroups, respectively, among other groups as members.

An aliphatic compound is a class of acyclic or cyclic, saturated orunsaturated, carbon compounds, excluding aromatic compounds, e.g., analiphatic compound is a non-aromatic organic compound. An “aliphaticgroup” is a generalized group formed by removing one or more hydrogenatoms (as necessary for the particular group) from a carbon atom of analiphatic compound. Aliphatic compounds and therefore aliphatic groupscan contain organic functional group(s) and/or atom(s) other than carbonand hydrogen.

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.,halogenated alkane indicates that the presence of one or more halogenatoms replacing an equivalent number of hydrogen atoms in the alkane).The term “alkyl group” is used herein in accordance with the definitionspecified by IUPAC: a univalent group formed by removing a hydrogen atomfrom an alkane. Similarly, an “alkylene group” refers to a group formedby removing two hydrogen atoms from an alkane (either two hydrogen atomsfrom one carbon atom or one hydrogen atom from two different carbonatoms). An “alkane group” is a general term that refers to a groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkane. An “alkyl group,” “alkylene group,”and “alkane group” can be acyclic or cyclic and/or linear or branchedunless otherwise specified. Primary, secondary, and tertiary alkylgroups are derived by removal of a hydrogen atom from a primary,secondary, and tertiary carbon atom, respectively, of an alkane. Then-alkyl group can be derived by removal of a hydrogen atom from aterminal carbon atom of a linear alkane. The groups RCH₂ (R≠H), R₂CH(R≠H), and R₃C (R≠H) are primary, secondary, and tertiary alkyl groups,respectively.

A cycloalkane is a saturated cyclic hydrocarbon, with or without sidechains, for example, cyclobutane. Other identifiers can be utilized toindicate the presence of particular groups in the cycloalkane (e.g.,halogenated cycloalkane indicates that the presence of one or morehalogen atoms replacing an equivalent number of hydrogen atoms in thecycloalkane). Unsaturated cyclic hydrocarbons having one endocyclicdouble or one triple bond are called cycloalkenes and cycloalkynes,respectively. Those having more than one such multiple bond arecycloalkadienes, cycloalkatrienes, and so forth. Other identifiers canbe utilized to indicate the presence of particular groups in thecycloalkenes, cycloalkadienes, cycloalkatrienes, and so forth.

A “cycloalkyl group” is a univalent group derived by removing a hydrogenatom from a ring carbon atom of a cycloalkane. For example, a1-methylcyclopropyl group and a 2-methylcyclopropyl group areillustrated as follows.

Similarly, a “cycloalkylene group” refers to a group derived by removingtwo hydrogen atoms from a cycloalkane, at least one of which is a ringcarbon. Thus, a “cycloalkylene group” includes a group derived from acycloalkane in which two hydrogen atoms are formally removed from thesame ring carbon, a group derived from a cycloalkane in which twohydrogen atoms are formally removed from two different ring carbons, anda group derived from a cycloalkane in which a first hydrogen atom isformally removed from a ring carbon and a second hydrogen atom isformally removed from a carbon atom that is not a ring carbon. A“cycloalkane group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group and atleast one of which is a ring carbon) from a cycloalkane.

The term “alkene” whenever used in this specification and claims refersa linear or branched hydrocarbon olefin that has one carbon-carbondouble bond and the general formula C_(n)H_(2n). Alkadienes refer to alinear or branched hydrocarbon olefin having two carbon-carbon doublebonds and the general formula C_(n)H_(2n-2), and alkatrienes refer tolinear or branched hydrocarbon olefins having three carbon-carbon andthe general formula C_(n)H_(2n-4). Alkenes, alkadienes, and alkatrienescan be further identified by the position of the carbon-carbon doublebond(s). Other identifiers can be utilized to indicate the presence orabsence of particular groups within an alkene, alkadiene, or alkatriene.For example, a haloalkene refers to an alkene having one or morehydrogen atoms replace with a halogen atom.

An “alkenyl group” is a univalent group derived from an alkene byremoval of a hydrogen atom from any carbon atom of the alkene. Thus,“alkenyl group” includes groups in which the hydrogen atom is formallyremoved from an sp² hybridized (olefinic) carbon atom and groups inwhich the hydrogen atom is formally removed from any other carbon atom.For example and unless otherwise specified, 1-propenyl (—CH═CHCH₃),2-propenyl (—CH₂CH═CH₂), and 3-butenyl (—CH₂CH₂CH═CH₂) groups areencompassed with the term “alkenyl group.” Similarly, an “alkenylenegroup” refers to a group formed by formally removing two hydrogen atomsfrom an alkene, either two hydrogen atoms from one carbon atom or onehydrogen atom from two different carbon atoms. An “alkene group” refersto a generalized group formed by removing one or more hydrogen atoms (asnecessary for the particular group) from an alkene. When the hydrogenatom is removed from a carbon atom participating in a carbon-carbondouble bond, the regiochemistry of the carbon from which the hydrogenatom is removed, and regiochemistry of the carbon-carbon double bond canboth be specified. Other identifiers can be utilized to indicate thepresence or absence of particular groups within an alkene group. Alkenegroups can also be further identified by the position of thecarbon-carbon double bond.

An arene is an aromatic hydrocarbon, with or without side chains (e.g.,benzene, toluene, or xylene, among others). An “aryl group” is a groupderived from the formal removal of a hydrogen atom from an aromatic ringcarbon of an arene. It should be noted that the arene can contain asingle aromatic hydrocarbon ring (e.g., benzene or toluene), containfused aromatic rings (e.g., naphthalene or anthracene), and contain oneor more isolated aromatic rings covalently linked via a bond (e.g.,biphenyl) or non-aromatic hydrocarbon group(s) (e.g., diphenylmethane).One example of an “aryl group” is ortho-tolyl (o-tolyl), the structureof which is shown here.

An “aralkyl group” is an aryl-substituted alkyl group having a freevalance at a non-aromatic carbon atom, for example, a benzyl group, or a2-phenyleth-lyl group, among others.

A “halide” has its usual meaning. Examples of halides include fluoride,chloride, bromide, and iodide.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer isderived from an olefin monomer and one olefin comonomer, while aterpolymer is derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers, terpolymers, etc.,derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene homopolymers,ethylene copolymers, ethylene terpolymers, and the like. As an example,an olefin copolymer, such as an ethylene copolymer, can be derived fromethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. Ifthe monomer and comonomer were ethylene and 1-hexene, respectively, theresulting polymer could be categorized an as ethylene/1-hexenecopolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process could involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene) to produce acopolymer.

The term “co-catalyst” is used generally herein to refer to compoundssuch as aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, organoaluminum compounds, organozinccompounds, organomagnesium compounds, organolithium compounds, and thelike, that can constitute one component of a catalyst composition, whenused, for example, in addition to an activator-support. The term“co-catalyst” is used regardless of the actual function of the compoundor any chemical mechanism by which the compound may operate.

The terms “chemically-treated solid oxide,” “treated solid oxidecompound,” and the like, are used herein to indicate a solid, inorganicoxide of relatively high porosity, which can exhibit Lewis acidic orBrønsted acidic behavior, and which has been treated with anelectron-withdrawing component, typically an anion, and which iscalcined. The electron-withdrawing component is typically anelectron-withdrawing anion source compound. Thus, the chemically-treatedsolid oxide can comprise a calcined contact product of at least onesolid oxide with at least one electron-withdrawing anion sourcecompound. Typically, the chemically-treated solid oxide comprises atleast one acidic solid oxide compound. The “activator-support” of thepresent invention can be a chemically-treated solid oxide. The terms“support” and “activator-support” are not used to imply these componentsare inert, and such components should not be construed as an inertcomponent of the catalyst composition. The term “activator,” as usedherein, refers generally to a substance that is capable of converting ametallocene component into a catalyst that can polymerize olefins, orconverting a contact product of a metallocene component and a componentthat provides an activatable ligand (e.g., an alkyl, a hydride) to themetallocene, when the metallocene compound does not already comprisesuch a ligand, into a catalyst that can polymerize olefins. This term isused regardless of the actual activating mechanism. Illustrativeactivators include activator-supports, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.Aluminoxanes, organoboron or organoborate compounds, and ionizing ioniccompounds generally are referred to as activators if used in a catalystcomposition in which an activator-support is not present. If thecatalyst composition contains an activator-support, then thealuminoxane, organoboron or organoborate, and ionizing ionic materialsare typically referred to as co-catalysts.

The term “fluoroorgano boron compound” is used herein with its ordinarymeaning to refer to neutral compounds of the form BY₃. The term“fluoroorgano borate compound” also has its usual meaning to refer tothe monoanionic salts of a fluoroorgano boron compound of the form[cation]⁺ [BY₄]⁻, where Y represents a fluorinated organic group.Materials of these types are generally and collectively referred to as“organoboron or organoborate compounds.”

The terms “metallocene,” “unbridged metallocene,” and “bridgedmetallocene,” as used herein, describe compounds comprising at least oneη³ to η⁵-cycloalkadienyl-type moiety, wherein η³ to η⁵-cycloalkadienylmoieties include cyclopentadienyl ligands, indenyl ligands, fluorenylligands, and the like, including partially saturated or substitutedderivatives or analogs of any of these. Possible substituents on theseligands may include H, therefore this invention comprises ligands suchas tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partiallysaturated indenyl, partially saturated fluorenyl, substituted partiallysaturated indenyl, substituted partially saturated fluorenyl, and thelike. In some contexts, the metallocene is referred to simply as the“catalyst,” in much the same way the term “co-catalyst” is used hereinto refer to, for example, an organoaluminum compound.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of theclaimed catalyst composition/mixture/system, the nature of the activecatalytic site, or the fate of the co-catalyst, the metallocenecompound(s), any olefin monomer used to prepare a precontacted mixture,or the activator (e.g., activator-support), after combining thesecomponents. Therefore, the terms “catalyst composition,” “catalystmixture,” “catalyst system,” and the like, encompass the initialstarting components of the composition, as well as whatever product(s)may result from contacting these initial starting components, and thisis inclusive of both heterogeneous and homogenous catalyst systems orcompositions. The terms “catalyst composition,” “catalyst mixture,”“catalyst system,” and the like, are used interchangeably throughoutthis disclosure.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions described herein. Combining additional materials orcomponents can be done by any suitable method. Further, the term“contact product” includes mixtures, blends, solutions, slurries,reaction products, and the like, or combinations thereof. Although“contact product” can include reaction products, it is not required forthe respective components to react with one another. Similarly, the term“contacting” is used herein to refer to materials which can be blended,mixed, slurried, dissolved, reacted, treated, or otherwise contacted insome other manner.

The term “precontacted” mixture is used herein to describe a firstmixture of catalyst components that are contacted for a first period oftime prior to the first mixture being used to form a “postcontacted” orsecond mixture of catalyst components that are contacted for a secondperiod of time. Typically, the precontacted mixture can describe amixture of a metallocene compound (one or more than one), olefin monomer(or monomers), and organoaluminum compound (or compounds), before thismixture is contacted with an activator-support(s) and optionaladditional organoaluminum compound. Thus, precontacted describescomponents that are used to contact each other, but prior to contactingthe components in the second, postcontacted mixture. Accordingly, thisinvention can occasionally distinguish between a component used toprepare the precontacted mixture and that component after the mixturehas been prepared. For example, according to this description, it ispossible for the precontacted organoaluminum compound, once it iscontacted with the metallocene compound and the olefin monomer, to havereacted to form at least one chemical compound, formulation, orstructure different from the distinct organoaluminum compound used toprepare the precontacted mixture. In this case, the precontactedorganoaluminum compound or component is described as comprising anorganoaluminum compound that was used to prepare the precontactedmixture.

Additionally, the precontacted mixture can describe a mixture ofmetallocene compound(s) and organoaluminum compound(s), prior tocontacting this mixture with an activator-support(s). This precontactedmixture also can describe a mixture of metallocene compound(s), olefinmonomer(s), and activator-support(s), before this mixture is contactedwith an organoaluminum co-catalyst compound or compounds.

Similarly, the term “postcontacted” mixture is used herein to describe asecond mixture of catalyst components that are contacted for a secondperiod of time, and one constituent of which is the “precontacted” orfirst mixture of catalyst components that were contacted for a firstperiod of time. Typically, the term “postcontacted” mixture is usedherein to describe the mixture of metallocene compound(s), olefinmonomer(s), organoaluminum compound(s), and activator-support(s) formedfrom contacting the precontacted mixture of a portion of thesecomponents with any additional components added to make up thepostcontacted mixture. Often, the activator-support can comprise achemically-treated solid oxide. For instance, the additional componentadded to make up the postcontacted mixture can be a chemically-treatedsolid oxide (one or more than one), and optionally, can include anorganoaluminum compound which is the same as or different from theorganoaluminum compound used to prepare the precontacted mixture, asdescribed herein. Accordingly, this invention can also occasionallydistinguish between a component used to prepare the postcontactedmixture and that component after the mixture has been prepared.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

Applicants disclose several types of ranges in the present invention.When Applicants disclose or claim a range of any type, Applicants'intent is to disclose or claim individually each possible number thatsuch a range could reasonably encompass, including end points of therange as well as any sub-ranges and combinations of sub-rangesencompassed therein. For example, when the Applicants disclose or claima chemical moiety having a certain number of carbon atoms, Applicants'intent is to disclose or claim individually every possible number thatsuch a range could encompass, consistent with the disclosure herein. Forexample, the disclosure that a moiety is a C₁ to C₁₈ hydrocarbyl group,or in alternative language, a hydrocarbyl group having from 1 to 18carbon atoms, as used herein, refers to a moiety that can be selectedindependently from a hydrocarbyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, as well as any rangebetween these two numbers (for example, a C₁ to C₈ hydrocarbyl group),and also including any combination of ranges between these two numbers(for example, a C₂ to C₄ and a C₁₂ to C₁₆ hydrocarbyl group).

Similarly, another representative example follows for the number-averagemolecular weight (Mn) of an olefin polymer produced in an aspect of thisinvention. By a disclosure that the Mn can be in a range from about8,000 to about 25,000 g/mol, Applicants intend to recite that the Mn canbe equal to about 8,000, about 9,000, about 10,000, about 11,000, about12,000, about 13,000, about 14,000, about 15,000, about 16,000, about17,000, about 18,000, about 19,000, about 20,000, about 21,000, about22,000, about 23,000, about 24,000, or about 25,000 g/mol. Additionally,the Mn can be within any range from about 8,000 to about 25,000 (forexample, from about 10,000 to about 22,000), and this also includes anycombination of ranges between about 8,000 and about 25,000 (for example,the Mn can be in a range from about 8,000 to about 10,000, or from about15,000 to about 25,000). Likewise, all other ranges disclosed hereinshould be interpreted in a manner similar to these two examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to new catalystcompositions, methods for preparing catalyst compositions, methods forusing the catalyst compositions to polymerize olefins, the polymerresins produced using such catalyst compositions, and articles producedusing these polymer resins. In particular, the present invention relatesto catalyst compositions containing three metallocene components and topolymerization processes utilizing such catalyst compositions.

Catalyst Component I

Catalyst component I can comprise an unbridged zirconium or hafniumbased metallocene compound and/or an unbridged zirconium and/or hafniumbased dinuclear metallocene compound. In one aspect, for instance,catalyst component I can comprise an unbridged zirconium or hafniumbased metallocene compound containing two cyclopentadienyl groups, twoindenyl groups, or a cyclopentadienyl and an indenyl group. In anotheraspect, catalyst component I can comprise an unbridged zirconium basedmetallocene compound containing two cyclopentadienyl groups, two indenylgroups, or a cyclopentadienyl and an indenyl group. In yet anotheraspect of this invention, catalyst component I can comprise an unbridgedmetallocene compound having formula (A):

Within formula (A), M¹, Cp^(A), Cp^(B), and each X are independentelements of the unbridged metallocene compound. Accordingly, theunbridged metallocene compound having formula (A) can be described usingany combination of M¹, Cp^(A), Cp^(B), and X disclosed herein.

Unless otherwise specified, formula (A) above, any other structuralformulas disclosed herein, and any metallocene complex, compound, orspecies disclosed herein are not designed to show stereochemistry orisomeric positioning of the different moieties (e.g., these formulas arenot intended to display cis or trans isomers, or R or Sdiastereoisomers), although such compounds are contemplated andencompassed by these formulas and/or structures.

In accordance with aspects of this invention, the metal in formula (A),M¹, can be Zr or Hf. In one aspect, for instance, M¹ can be Zr, while inanother aspect, M¹ can be Hf.

Each X in formula (A) independently can be a monoanionic ligand. In someaspects, suitable monoanionic ligands can include, but are not limitedto, H (hydride), BH₄, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, a C₁ to C₃₆ hydrocarbylaminyl group, a C₁ to C₃₆hydrocarbylsilyl group, a C₁ to C₃₆ hydrocarbylaminylsilyl group, —OBR¹₂, or —OSO₂R¹, wherein R¹ is a C₁ to C₃₆ hydrocarbyl group. It iscontemplated that each X can be either the same or a differentmonoanionic ligand.

In one aspect, each X independently can be H, BH₄, a halide (e.g., F,Cl, Br, etc.), a C₁ to C₁₈ hydrocarbyl group, a C₁ to C₁₈ hydrocarboxygroup, a C₁ to C₁₈ hydrocarbylaminyl group, a C₁ to C₁₈ hydrocarbylsilylgroup, or a C₁ to C₁₈ hydrocarbylaminylsilyl group. Alternatively, eachX independently can be H, BH₄, a halide, OBR¹ ₂, or OSO₂R¹, wherein R¹is a C₁ to C₁₈ hydrocarbyl group. In another aspect, each Xindependently can be H, BH₄, a halide, a C₁ to C₁₂ hydrocarbyl group, aC₁ to C₁₂ hydrocarboxy group, a C₁ to C₁₂ hydrocarbylaminyl group, a C₁to C₁₂ hydrocarbylsilyl group, a C₁ to C₁₂ hydrocarbylaminylsilyl group,OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ to C₁₂ hydrocarbyl group. Inanother aspect, each X independently can be H, BH₄, a halide, a C₁ toC₁₀ hydrocarbyl group, a C₁ to C₁₀ hydrocarboxy group, a C₁ to C₁₀hydrocarbylaminyl group, a C₁ to C₁₀ hydrocarbylsilyl group, a C₁ to C₁₀hydrocarbylaminylsilyl group, OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ toC₁₀ hydrocarbyl group. In yet another aspect, each X independently canbe H, BH₄, a halide, a C₁ to C₈ hydrocarbyl group, a C₁ to C₈hydrocarboxy group, a C₁ to C₈ hydrocarbylaminyl group, a C₁ to C₈hydrocarbylsilyl group, a C₁ to C₈ hydrocarbylaminylsilyl group, OBR¹ ₂,or OSO₂R¹, wherein R¹ is a C₁ to C₈ hydrocarbyl group. In still anotheraspect, each X independently can be a halide or a C₁ to C₁₈ hydrocarbylgroup. For example, each X can be Cl.

The hydrocarbyl group which can be an X in formula (A) can be a C₁ toC₃₆ hydrocarbyl group, including, but not limited to, a C₁ to C₃₆ alkylgroup, a C₂ to C₃₆ alkenyl group, a C₄ to C₃₆ cycloalkyl group, a C₆ toC₃₆ aryl group, or a C₇ to C₃₆ aralkyl group. For instance, each Xindependently can be a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenyl group,a C₄ to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, or a C₇ to C₁₈aralkyl group; alternatively, each X independently can be a C₁ to C₁₂alkyl group, a C₂ to C₁₂ alkenyl group, a C₄ to C₁₂ cycloalkyl group, aC₆ to C₁₂ aryl group, or a C₇ to C₁₂ aralkyl group; alternatively, eachX independently can be a C₁ to C₁₀ alkyl group, a C₂ to C₁₀ alkenylgroup, a C₄ to C₁₀ cycloalkyl group, a C₆ to C₁₀ aryl group, or a C₇ toC₁₀ aralkyl group; or alternatively, each X independently can be a C₁ toC₅ alkyl group, a C₂ to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, aC₆ to C₈ aryl group, or a C₇ to C₈ aralkyl group.

Accordingly, in some aspects, the alkyl group which can be an X informula (A) can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, a undecyl group, a dodecyl group, atridecyl group, a tetradecyl group, a pentadecyl group, a hexadecylgroup, a heptadecyl group, or an octadecyl group; or alternatively, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, ora decyl group. In some aspects, the alkyl group which can be an X informula (A) can be a methyl group, an ethyl group, a n-propyl group, aniso-propyl group, a n-butyl group, an iso-butyl group, a sec-butylgroup, a tert-butyl group, a n-pentyl group, an iso-pentyl group, asec-pentyl group, or a neopentyl group; alternatively, a methyl group,an ethyl group, an iso-propyl group, a tert-butyl group, or a neopentylgroup; alternatively, a methyl group; alternatively, an ethyl group;alternatively, a n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.

Suitable alkenyl groups which can be an X in formula (A) can include,but are not limited to, an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, a decenyl group, a undecenyl group, a dodecenylgroup, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, ahexadecenyl group, a heptadecenyl group, or an octadecenyl group. Suchalkenyl groups can be linear or branched, and the double bond can belocated anywhere in the chain. In one aspect, each X in formula (A)independently can be an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, or a decenyl group, while in another aspect,each X in formula (A) independently can be an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, or a hexenyl group. Forexample, an X can be an ethenyl group; alternatively, a propenyl group;alternatively, a butenyl group; alternatively, a pentenyl group; oralternatively, a hexenyl group. In yet another aspect, an X can be aterminal alkenyl group, such as a C₃ to C₁₈ terminal alkenyl group, a C₃to C₁₂ terminal alkenyl group, or a C₃ to C₈ terminal alkenyl group.Illustrative terminal alkenyl groups can include, but are not limitedto, a prop-2-en-1-yl group, a bute-3-en-1-yl group, a pent-4-en-1-ylgroup, a hex-5-en-1-yl group, a hept-6-en-1-yl group, an octe-7-en-1-ylgroup, a non-8-en-1-yl group, a dece-9-en-1-yl group, and so forth.

Each X in formula (A) can be a cycloalkyl group, including, but notlimited to, a cyclobutyl group, a substituted cyclobutyl group, acyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group,a substituted cyclohexyl group, a cycloheptyl group, a substitutedcycloheptyl group, a cyclooctyl group, or a substituted cyclooctylgroup. For example, an X in formula (A) can be a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group. Moreover, each X in formula (A) independently can be acyclobutyl group or a substituted cyclobutyl group; alternatively, acyclopentyl group or a substituted cyclopentyl group; alternatively, acyclohexyl group or a substituted cyclohexyl group; alternatively, acycloheptyl group or a substituted cycloheptyl group; alternatively, acyclooctyl group or a substituted cyclooctyl group; alternatively, acyclopentyl group; alternatively, a substituted cyclopentyl group;alternatively, a cyclohexyl group; or alternatively, a substitutedcyclohexyl group. Substituents which can be utilized for the substitutedcycloalkyl group are independently disclosed herein and can be utilizedwithout limitation to further describe the substituted cycloalkyl groupwhich can be an X in formula (A).

In some aspects, the aryl group which can be an X in formula (A) can bea phenyl group, a substituted phenyl group, a naphthyl group, or asubstituted naphthyl group. In an aspect, the aryl group can be a phenylgroup or a substituted phenyl group; alternatively, a naphthyl group ora substituted naphthyl group; alternatively, a phenyl group or anaphthyl group; alternatively, a substituted phenyl group or asubstituted naphthyl group; alternatively, a phenyl group; oralternatively, a naphthyl group. Substituents which can be utilized forthe substituted phenyl groups or substituted naphthyl groups areindependently disclosed herein and can be utilized without limitation tofurther describe the substituted phenyl groups or substituted naphthylgroups which can be an X in formula (A).

In an aspect, the substituted phenyl group which can be an X in formula(A) can be a 2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other aspects, the substitutedphenyl group can be a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.Substituents which can be utilized for these specific substituted phenylgroups are independently disclosed herein and can be utilized withoutlimitation to further describe these substituted phenyl groups which canbe an X group(s) in formula (A).

In some aspects, the aralkyl group which can be an X group in formula(A) can be a benzyl group or a substituted benzyl group. In an aspect,the aralkyl group can be a benzyl group or, alternatively, a substitutedbenzyl group. Substituents which can be utilized for the substitutedaralkyl group are independently disclosed herein and can be utilizedwithout limitation to further describe the substituted aralkyl groupwhich can be an X group(s) in formula (A).

In an aspect, each non-hydrogen substituent(s) for the substitutedcycloalkyl group, substituted aryl group, or substituted aralkyl groupwhich can be an X in formula (A) independently can be a C₁ to C₁₈hydrocarbyl group; alternatively, a C₁ to C₈ hydrocarbyl group; oralternatively, a C₁ to C₅ hydrocarbyl group. Specific hydrocarbyl groupsare independently disclosed herein and can be utilized withoutlimitation to further describe the substituents of the substitutedcycloalkyl groups, substituted aryl groups, or substituted aralkylgroups which can be an X in formula (A). For instance, the hydrocarbylsubstituent can be an alkyl group, such as a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, asec-butyl group, an isobutyl group, a tert-butyl group, a n-pentylgroup, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, atert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group,or a neo-pentyl group, and the like. Furthermore, the hydrocarbylsubstituent can be a benzyl group, a phenyl group, a tolyl group, or axylyl group, and the like.

A hydrocarboxy group is used generically herein to include, forinstance, alkoxy, aryloxy, aralkoxy, -(alkyl, aryl, oraralkyl)-O-(alkyl, aryl, or aralkyl) groups, and —O(CO)-(hydrogen orhydrocarbyl) groups, and these groups can comprise up to about 36 carbonatoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ to C₁₀, or C₁ to C₈ hydrocarboxygroups). Illustrative and non-limiting examples of hydrocarboxy groupswhich can be an X in formula (A) can include, but are not limited to, amethoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxygroup, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a2-methyl-1-butoxy group, a tert-pentoxy group, a 3-methyl-1-butoxygroup, a 3-methyl-2-butoxy group, a neo-pentoxy group, a phenoxy group,a toloxy group, a xyloxy group, a 2,4,6-trimethylphenoxy group, abenzoxy group, an acetylacetonate group (acac), a formate group, anacetate group, a stearate group, an oleate group, a benzoate group, andthe like. In an aspect, the hydrocarboxy group which can be an X informula (A) can be a methoxy group; alternatively, an ethoxy group;alternatively, an n-propoxy group; alternatively, an isopropoxy group;alternatively, an n-butoxy group; alternatively, a sec-butoxy group;alternatively, an isobutoxy group; alternatively, a tert-butoxy group;alternatively, an n-pentoxy group; alternatively, a 2-pentoxy group;alternatively, a 3-pentoxy group; alternatively, a 2-methyl-1-butoxygroup; alternatively, a tert-pentoxy group; alternatively, a3-methyl-1-butoxy group, alternatively, a 3-methyl-2-butoxy group;alternatively, a neo-pentoxy group; alternatively, a phenoxy group;alternatively, a toloxy group; alternatively, a xyloxy group;alternatively, a 2,4,6-trimethylphenoxy group; alternatively, a benzoxygroup; alternatively, an acetylacetonate group; alternatively, a formategroup; alternatively, an acetate group; alternatively, a stearate group;alternatively, an oleate group; or alternatively, a benzoate group.

The term hydrocarbylaminyl group is used generically herein to refercollectively to, for instance, alkylaminyl, arylaminyl, aralkylaminyl,dialkylaminyl, diarylaminyl, diaralkylaminyl, and -(alkyl, aryl, oraralkyl)-N-(alkyl, aryl, or aralkyl) groups, and unless otherwisespecified, the hydrocarbylaminyl groups which can be an X in formula (A)can comprise up to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁to C₁₀, or C₁ to C₈ hydrocarbylaminyl groups). Accordingly,hydrocarbylaminyl is intended to cover both (mono)hydrocarbylaminyl anddihydrocarbylaminyl groups. In some aspects, the hydrocarbylaminyl groupwhich can be an X in formula (A) can be, for instance, a methylaminylgroup (—NHCH₃), an ethylaminyl group (—NHCH₂CH₃), an n-propylaminylgroup (—NHCH₂CH₂CH₃), an iso-propylaminyl group (—NHCH(CH₃)₂), ann-butylaminyl group (—NHCH₂CH₂CH₂CH₃), a t-butylaminyl group(—NHC(CH₃)₃), an n-pentylaminyl group (—NHCH₂CH₂CH₂CH₂CH₃), aneo-pentylaminyl group (—NHCH₂C(CH₃)₃), a phenylaminyl group (—NHC₆H₅),a tolylaminyl group (—NHC₆H₄CH₃), or a xylylaminyl group(—NHC₆H₃(CH₃)₂); alternatively, a methylaminyl group; alternatively, anethylaminyl group; alternatively, a propylaminyl group; oralternatively, a phenylaminyl group. In other aspects, thehydrocarbylaminyl group which can be an X in formula (A) can be, forinstance, a dimethylaminyl group (—N(CH₃)₂), a diethylaminyl group(—N(CH₂CH₃)₂), a di-n-propylaminyl group (—N(CH₂CH₂CH₃)₂), adi-iso-propylaminyl group (—N(CH(CH₃)₂)₂), a di-n-butylaminyl group(—N(CH₂CH₂CH₂CH₃)₂), a di-t-butylaminyl group (—N(C(CH₃)₃)₂), adi-n-pentylaminyl group (—N(CH₂CH₂CH₂CH₂CH₃)₂), a di-neo-pentylaminylgroup (—N(CH₂C(CH₃)₃)₂), a di-phenylaminyl group (—N(C₆H₅)₂), adi-tolylaminyl group (—N(C₆H₄—CH₃)₂), or a di-xylylaminyl group(—N(C₆H₃(CH₃)₂)₂); alternatively, a dimethylaminyl group; alternatively,a di-ethylaminyl group; alternatively, a di-n-propylaminyl group; oralternatively, a di-phenylaminyl group.

In accordance with some aspects disclosed herein, each X independentlycan be a C₁ to C₃₆ hydrocarbylsilyl group; alternatively, a C₁ to C₂₄hydrocarbylsilyl group; alternatively, a C₁ to C₁₈ hydrocarbylsilylgroup; or alternatively, a C₁ to C₈ hydrocarbylsilyl group. In anaspect, each hydrocarbyl (one or more) of the hydrocarbylsilyl group canbe any hydrocarbyl group disclosed herein (e.g., a C₁ toC_(alkyl group, a C) ₂ to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group,a C₆ to C₈ aryl group, a C₇ to C₈ aralkyl group, etc.). As used herein,hydrocarbylsilyl is intended to cover (mono)hydrocarbylsilyl (—SiH₂R),dihydrocarbylsilyl (—SiHR₂), and trihydrocarbylsilyl (—SiR₃) groups,with R being a hydrocarbyl group. In one aspect, the hydrocarbylsilylgroup can be a C₃ to C₃₆ or a C₃ to C₁₈ trihydrocarbylsilyl group, suchas, for example, a trialkylsilyl group or a triphenylsilyl group.Illustrative and non-limiting examples of hydrocarbylsilyl groups whichcan be an X group(s) in formula (A) can include, but are not limited to,trimethylsilyl, triethylsilyl, tripropylsilyl (e.g., triisopropylsilyl),tributylsilyl, tripentylsilyl, triphenylsilyl, allyldimethylsilyl, andthe like.

A hydrocarbylaminylsilyl group is used herein to refer to groupscontaining at least one hydrocarbon moiety, at least one N atom, and atleast one Si atom. Illustrative and non-limiting examples ofhydrocarbylaminylsilyl groups which can be an X can include, but are notlimited to —N(SiMe₃)₂, —N(SiEt₃)₂, and the like. Unless otherwisespecified, the hydrocarbylaminylsilyl groups which can be X can compriseup to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ to C₁₂, orC₁ to C₈ hydrocarbylaminylsilyl groups). In an aspect, each hydrocarbyl(one or more) of the hydrocarbylaminylsilyl group can be any hydrocarbylgroup disclosed herein (e.g., a C₁ to C₅ alkyl group, a C₂ to C₅ alkenylgroup, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, a C₇ to C₈aralkyl group, etc.). Moreover, hydrocarbylaminylsilyl is intended tocover —NH(SiH₂R), —NH(SiHR₂), —NH(SiR₃), —N(SiH₂R)₂, —N(SiHR₂)₂, and—N(SiR₃)₂ groups, among others, with R being a hydrocarbyl group.

In an aspect, each X independently can be —OBR¹ ₂ or —OSO₂R¹, wherein R¹is a C₁ to C₃₆ hydrocarbyl group, or alternatively, a C₁ to C₁₈hydrocarbyl group. The hydrocarbyl group in OBR¹ ₂ and/or OSO₂R¹independently can be any hydrocarbyl group disclosed herein, such as,for instance, a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenyl group, a C₄to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, or a C₇ to C₁₈ aralkylgroup; alternatively, a C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenylgroup, a C₄ to C₁₂ cycloalkyl group, a C₆ to C₁₂ aryl group, or a C₇ toC₁₂ aralkyl group; or alternatively, a C₁ to C₈ alkyl group, a C₂ to C₈alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or aC₇ to C₈ aralkyl group.

In one aspect, each X independently can be H, BH₄, a halide, or a C₁ toC₃₆ hydrocarbyl group, hydrocarboxy group, hydrocarbylaminyl group,hydrocarbylsilyl group, or hydrocarbylaminylsilyl group, while inanother aspect, each X independently can be H, BH₄, or a C₁ to C₁₈hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group, orhydrocarbylaminylsilyl group. In yet another aspect, each Xindependently can be a halide; alternatively, a C₁ to C₁₈ hydrocarbylgroup; alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, aC₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group. In still another aspect, each X can be H;alternatively, F; alternatively, Cl; alternatively, Br; alternatively,I; alternatively, BH₄; alternatively, a C₁ to C₁₈ hydrocarbyl group;alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, a C₁ toC₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈ hydrocarbylsilylgroup; or alternatively, a C₁ to C₁₈ hydrocarbylaminylsilyl group.

Each X independently can be, in some aspects, H, a halide, methyl,phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, formate,acetate, stearate, oleate, benzoate, an alkylaminyl, a dialkylaminyl, atrihydrocarbylsilyl, or a hydrocarbylaminylsilyl; alternatively, H, ahalide, methyl, phenyl, or benzyl; alternatively, an alkoxy, an aryloxy,or acetylacetonate; alternatively, an alkylaminyl or a dialkylaminyl;alternatively, a trihydrocarbylsilyl or hydrocarbylaminylsilyl;alternatively, H or a halide; alternatively, methyl, phenyl, benzyl, analkoxy, an aryloxy, acetylacetonate, an alkylaminyl, or a dialkylaminyl;alternatively, H; alternatively, a halide; alternatively, methyl;alternatively, phenyl; alternatively, benzyl; alternatively, an alkoxy;alternatively, an aryloxy; alternatively, acetylacetonate;alternatively, an alkylaminyl; alternatively, a dialkylaminyl;alternatively, a trihydrocarbylsilyl; or alternatively, ahydrocarbylaminylsilyl. In these and other aspects, the alkoxy, aryloxy,alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, andhydrocarbylaminylsilyl can be a C₁ to C₃₆, a C₁ to C₁₈, a C₁ to C₁₂, ora C₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, and hydrocarbylaminylsilyl.

Moreover, each X independently can be, in certain aspects, a halide or aC₁ to CH hydrocarbyl group; alternatively, a halide or a C₁ to C₈hydrocarbyl group; alternatively, F, Cl, Br, I, methyl, benzyl, orphenyl; alternatively, Cl, methyl, benzyl, or phenyl; alternatively, aC₁ to C₁₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; alternatively, aC₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; or alternatively,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, benzyl, naphthyl, trimethylsilyl,triisopropylsilyl, triphenylsilyl, or allyldimethylsilyl.

In formula (A), Cp^(A) and Cp^(B) independently can be a substituted orunsubstituted cyclopentadienyl or indenyl group. In one aspect, Cp^(A)and Cp^(B) independently can be an unsubstituted cyclopentadienyl orindenyl group. Alternatively, Cp^(A) and Cp^(B) independently can be asubstituted indenyl or cyclopentadienyl group, for example, having up to5 substituents.

If present, each substituent on Cp^(A) and Cp^(B) independently can beH, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenatedhydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆hydrocarbylsilyl group. Importantly, each substituent on Cp^(A) and/orCp^(B) can be either the same or a different substituent group.Moreover, each substituent can be at any position on the respectivecyclopentadienyl or indenyl ring structure that conforms with the rulesof chemical valence. In an aspect, the number of substituents on Cp^(A)and/or on Cp^(B) and/or the positions of each substituent on Cp^(A)and/or on Cp^(B) are independent of each other. For instance, two ormore substituents on Cp^(A) can be different, or alternatively, eachsubstituent on Cp^(A) can be the same. Additionally or alternatively,two or more substituents on Cp^(B) can be different, or alternatively,all substituents on Cp^(B) can be the same. In another aspect, one ormore of the substituents on Cp^(A) can be different from the one or moreof the substituents on Cp^(B), or alternatively, all substituents onboth Cp^(A) and/or on Cp^(B) can be the same. In these and otheraspects, each substituent can be at any position on the respectivecyclopentadienyl or indenyl ring structure. If substituted, Cp^(A)and/or Cp^(B) independently can have one substituent, two substituents,three substituents, four substituents, and so forth.

In formula (A), each substituent on Cp^(A) and/or on Cp^(B)independently can be H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ toC₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or aC₁ to C₃₆ hydrocarbylsilyl group. In some aspects, each substituentindependently can be H; alternatively, a halide; alternatively, a C₁ toC₁₈ hydrocarbyl group; alternatively, a C₁ to C₁₈ halogenatedhydrocarbyl group; alternatively, a C₁ to C₁₈ hydrocarboxy group;alternatively, a C₁ to C₁₈ hydrocarbylsilyl group; alternatively, a C₁to C₁₂ hydrocarbyl group or a C₁ to C₁₂ hydrocarbylsilyl group; oralternatively, a C₁ to C₈ alkyl group or a C₃ to C₈ alkenyl group. Thehalide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, andC₁ to C₃₆ hydrocarbylsilyl group which can be a substituent on Cp^(A)and/or on Cp^(B) in formula (A) can be any halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ hydrocarboxy group, and C₁ to C₃₆ hydrocarbylsilylgroup described herein (e.g., as pertaining to X in formula (A)). Asubstituent on Cp^(A) and/or on Cp^(B) in formula (A) can be, in certainaspects, a C₁ to C₃₆ halogenated hydrocarbyl group, where thehalogenated hydrocarbyl group indicates the presence of one or morehalogen atoms replacing an equivalent number of hydrogen atoms in thehydrocarbyl group. The halogenated hydrocarbyl group often can be ahalogenated alkyl group, a halogenated alkenyl group, a halogenatedcycloalkyl group, a halogenated aryl group, or a halogenated aralkylgroup. Representative and non-limiting halogenated hydrocarbyl groupsinclude pentafluorophenyl, trifluoromethyl (CF₃), and the like.

As a non-limiting example, if present, each substituent on Cp^(A) and/orCp^(B) independently can be H, Cl, CF₃, a methyl group, an ethyl group,a propyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group, anethenyl group, a propenyl group, a butenyl group, a pentenyl group, ahexenyl group, a heptenyl group, an octenyl group, a nonenyl group, adecenyl group, a phenyl group, a tolyl group (or other substituted arylgroup), a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group; alternatively, H; alternatively, Cl;alternatively, CF₃; alternatively, a methyl group; alternatively, anethyl group; alternatively, a propyl group; alternatively, a butylgroup; alternatively, a pentyl group; alternatively, a hexyl group;alternatively, a heptyl group; alternatively, an octyl group, a nonylgroup; alternatively, a decyl group; alternatively, an ethenyl group;alternatively, a propenyl group; alternatively, a butenyl group;alternatively, a pentenyl group; alternatively, a hexenyl group;alternatively, a heptenyl group; alternatively, an octenyl group;alternatively, a nonenyl group; alternatively, a decenyl group;alternatively, a phenyl group; alternatively, a tolyl group;alternatively, a benzyl group; alternatively, a naphthyl group;alternatively, a trimethylsilyl group; alternatively, atriisopropylsilyl group; alternatively, a triphenylsilyl group; oralternatively, an allyldimethylsilyl group.

Illustrative and non-limiting examples of unbridged metallocenecompounds having formula (A) and/or suitable for use as catalystcomponent I can include the following compounds:

and the like, as well as combinations thereof.

Further examples of unbridged metallocene compounds having formula (A)and/or suitable for use as catalyst component I can include, but are notlimited to, the following compounds:

and the like, as well as combinations thereof.

Additional non-limiting examples of unbridged metallocene compoundshaving formula (A) and/or suitable for use as catalyst component I caninclude the following compounds:

and the like, as well as combinations thereof.

Catalyst component I is not limited solely to unbridged metallocenecompounds such as described above. For example, catalyst component I cancomprise an unbridged zirconium and/or hafnium based dinuclearmetallocene compound. In one aspect, catalyst component I can comprisean unbridged zirconium based homodinuclear metallocene compound. Inanother aspect, catalyst component I can comprise an unbridged hafniumbased homodinuclear metallocene compound. In yet another aspect,catalyst component I can comprise an unbridged zirconium and/or hafniumbased heterodinuclear metallocene compound (i.e., dinuclear compoundwith two hafniums, or two zirconiums, or one zirconium and one hafnium).Catalyst component I can comprise unbridged dinuclear metallocenes suchas those described in U.S. Pat. Nos. 7,919,639 and 8,080,681, thedisclosures of which are incorporated herein by reference in theirentirety. Illustrative and non-limiting examples of dinuclearmetallocene compounds suitable for use as catalyst component I caninclude the following compounds:

and the like, as well as combinations thereof

Catalyst Component II

Catalyst component II can comprise a bridged zirconium based metallocenecompound with a fluorenyl group, and with no aryl groups on the bridginggroup. In one aspect, for instance, catalyst component II can comprise abridged zirconium based metallocene compound with a cyclopentadienylgroup and a fluorenyl group, and with no aryl groups on the bridginggroup. In another aspect, catalyst component II can comprise a bridgedmetallocene compound having formula (B):

Within formula (B), Cp^(C), each X, E², R^(X), and R^(Y) are independentelements of the bridged metallocene compound. Accordingly, the bridgedmetallocene compound having formula (B) can be described using anycombination of Cp^(C), X, E², R^(X), and R^(Y) disclosed herein.

The selections for each X in formula (B) are the same as those describedherein above for formula (A). In formula (B), Cp^(C) can be asubstituted cyclopentadienyl, indenyl, or fluorenyl group. In oneaspect, Cp^(C) can be a substituted cyclopentadienyl group, while inanother aspect, Cp^(C) can be a substituted indenyl group.

In some aspects, Cp^(C) can contain no additional substituents, e.g.,other than bridging group E², discussed further herein below. In otheraspects, Cp^(C) can be further substituted with one substituent, twosubstituents, three substituents, four substituents, and so forth. Ifpresent, each substituent on Cp^(C) independently can be H, a halide, aC₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group,a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group.Importantly, each substituent on Cp^(C) can be either the same or adifferent substituent group. Moreover, each substituent can be at anyposition on the respective cyclopentadienyl, indenyl, or fluorenyl ringstructure that conforms with the rules of chemical valence. In general,any substituent on Cp^(C), independently, can be H or any halide, C₁ toC₃₆ hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ toC₃₆ hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl group describedherein (e.g., as pertaining to substituents on Cp^(A) and Cp^(B) informula (A)).

In one aspect, for example, each substituent on Cp^(C) independently canbe a C₁ to C₁₂ hydrocarbyl group or a C₁ to C₁₂ hydrocarbylsilyl group.In another aspect, each substituent on Cp^(C) independently can be a C₁to C₈ alkyl group or a C₃ to C₈ alkenyl group. In yet another aspect,each substituent on Cp^(C) independently can be H, C₁, CF₃, a methylgroup, an ethyl group, a propyl group, a butyl group, a pentyl group, ahexyl group, a heptyl group, an octyl group, a nonyl group, a decylgroup, an ethenyl group, a propenyl group, a butenyl group, a pentenylgroup, a hexenyl group, a heptenyl group, an octenyl group, a nonenylgroup, a decenyl group, a phenyl group, a tolyl group, a benzyl group, anaphthyl group, a trimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, or an allyldimethylsilyl group.

Similarly, R^(X) and R^(Y) in formula (B) independently can be H or anyhalide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbylgroup, C₁ to C₃₆ hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl groupdisclosed herein (e.g., as pertaining to substituents on Cp^(A) andCp^(B) in formula (A)). In one aspect, for example, R^(X) and R^(Y)independently can be H or a C₁ to C₁₂ hydrocarbyl group. In anotheraspect, R^(X) and R^(Y) independently can be a C₁ to C₁₀ hydrocarbylgroup. In yet another aspect, R^(X) and R^(Y) independently can be H,C₁, CF₃, a methyl group, an ethyl group, a propyl group, a butyl group(e.g., t-Bu), a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, an ethenyl group, a propenyl group,a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolylgroup, a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group, and the like. In still another aspect, R^(X)and R^(Y) independently can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, a hexenyl group, a heptenylgroup, an octenyl group, a nonenyl group, a decenyl group, a phenylgroup, a tolyl group, or a benzyl group.

Bridging group E² in formula (B) can be (i) a bridging group having theformula >E^(A)R^(A)R^(B), wherein E^(A) can be C, Si, or Ge, and R^(A)and R^(B) independently can be H or a C₁ to C₁₈ hydrocarbyl group; (ii)a bridging group having the formula —CR^(C)R^(D)—CR^(E)R^(F)—, whereinR^(C), R^(D), R^(E), and R^(E) independently can H or a C₁ to C₁₈hydrocarbyl group; or (iii) a bridging group having the formula—SiR^(G)R^(H)-E⁵R^(I)R^(J)—, wherein E⁵ can be C or Si, and R^(G),R^(H), R^(I), and R^(J) independently can be H or a C₁ to C₁₈hydrocarbyl group. In these formulas, R^(A), R^(B), R^(C), R^(D), R^(E),R^(E), R^(G), R^(H), R^(I), and R^(J) are not aryl groups.

In the first option, the bridging group E² can have the formula>E^(A)R^(A)R^(B), wherein E^(A) can be C, Si, or Ge, and R^(A) and R^(B)independently can be H or any C₁ to C₁₈ hydrocarbyl group disclosedherein (i.e., other than an aryl group). In some aspects of thisinvention, R^(A) and R^(B) independently can be a C₁ to C₁₂ hydrocarbylgroup; alternatively, R^(A) and R^(B) independently can be a C₁ to C₈hydrocarbyl group; alternatively, R^(A) and R^(B) independently can be aC₁ to C₈ alkyl group or a C₃ to C₈ alkenyl group; alternatively, R^(A)and R^(B) independently can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, a hexenyl group, a heptenylgroup, an octenyl group, a nonenyl group, or a decenyl group; oralternatively, R^(A) and R^(B) independently can be a methyl group, anethyl group, a propyl group, a butyl group, a pentyl group, a hexylgroup, a propenyl group, a butenyl group, a pentenyl group, or a hexenylgroup. In these and other aspects, R^(A) and R^(B) can be either thesame or different.

In the second option, the bridging group E² can have the formula—CR^(C)R^(D)—CR^(E)R^(E)—, wherein R^(C), R^(D), R^(E), and R^(E)independently can be H or any C₁ to C₁₈ hydrocarbyl group disclosedherein (i.e., other than an aryl group). For instance, R^(C), R^(D),R^(E), and R^(E) independently can be H or a methyl group.

In the third option, the bridging group E² can have the formula—SiR^(G)R^(H)-E⁵R^(I)R^(J)—, wherein E⁵ can be C or Si, and R^(G),R^(H), R^(I), and R^(J) independently can be H or any C₁ to C₁₈hydrocarbyl group disclosed herein (i.e., other than an aryl group). Forinstance, E⁵ can be Si, and R^(G), R^(H), R^(I), and R^(J) independentlycan be H or a methyl group.

Illustrative and non-limiting examples of bridged metallocene compoundshaving formula (B) and/or suitable for use as catalyst component II caninclude the following compounds (Me=methyl, t-Bu=tert-butyl):

and the like, as well as combinations thereof.

Further examples of bridged metallocene compounds having formula (B)and/or suitable for use as catalyst component II can include, but arenot limited to, the following compounds:

and the like, as well as combinations thereof.

Catalyst Component III

Catalyst component III can comprise a bridged zirconium or hafnium basedmetallocene compound with a fluorenyl group, and an aryl group on thebridging group. In one aspect, for instance, catalyst component III cancomprise a bridged zirconium or hafnium based metallocene compound witha cyclopentadienyl group and fluorenyl group, and an aryl group on thebridging group. In another aspect, catalyst component III can comprise abridged zirconium based metallocene compound with a fluorenyl group, andan aryl group on the bridging group, while in yet another aspect,catalyst component III can comprise a bridged hafnium based metallocenecompound with a fluorenyl group, and an aryl group on the bridginggroup. In these and other aspects, the aryl group on the bridging groupcan be a phenyl group.

Catalyst component III can comprise a bridged metallocene compoundhaving formula (C) in certain aspects of this invention:

Within formula (C), M³, Cp^(C), R^(X), R^(Y), E³, each R³, and each Xare independent elements of the bridged metallocene compound.Accordingly, the bridged metallocene compound having formula (C) can bedescribed using any combination of M³, Cp^(C), R^(X), R^(Y), E³, R³, andX disclosed herein.

As noted above and unless otherwise specified, formula (C) above, anyother structural formulas disclosed herein, and any metallocene (ordinuclear metallocene) complex, compound, or species disclosed hereinare not designed to show stereochemistry or isomeric positioning of thedifferent moieties (e.g., these formulas are not intended to display cisor trans isomers, or R or S diastereoisomers), although such compoundsare contemplated and encompassed by these formulas and/or structures.

The selections for Cp^(C), Rx, R^(Y), and each X in formula (C) are thesame as those described herein above for formula (B). Hence, in formula(C), Cp^(C) can be a substituted cyclopentadienyl, indenyl, or fluorenylgroup. In some aspects, Cp^(C) can be a substituted cyclopentadienylgroup, while in other aspects, Cp^(C) can be a substituted indenylgroup. Cp^(C) can contain no additional substituents, e.g., other thanbridging group E³, discussed further herein below. Alternatively, Cp^(C)can be further substituted with one substituent, two substituents, threesubstituents, four substituents, and so forth. If present, eachsubstituent on Cp^(C) independently can be H, a halide, a C₁ to C₃₆hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group.Importantly, each substituent on Cp^(C) can be either the same or adifferent substituent group. Moreover, each substituent can be at anyposition on the respective cyclopentadienyl, indenyl, or fluorenyl ringstructure that conforms with the rules of chemical valence. In general,any substituent on Cp^(C), independently, can be H or any halide, C₁ toC₃₆ hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ toC₃₆ hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl group describedherein (e.g., as pertaining to substituents on Cp^(A) and Cp^(B) informula (A)).

In one aspect, for example, each substituent on Cp^(C) independently canbe a C₁ to C₁₂ hydrocarbyl group or a C₁ to C₁₂ hydrocarbylsilyl group.In another aspect, each substituent on Cp^(C) independently can be a C₁to C₈ alkyl group or a C₃ to C₈ alkenyl group. In yet another aspect,each substituent on Cp^(C) independently can be H, C₁, CF₃, a methylgroup, an ethyl group, a propyl group, a butyl group, a pentyl group, ahexyl group, a heptyl group, an octyl group, a nonyl group, a decylgroup, an ethenyl group, a propenyl group, a butenyl group, a pentenylgroup, a hexenyl group, a heptenyl group, an octenyl group, a nonenylgroup, a decenyl group, a phenyl group, a tolyl group, a benzyl group, anaphthyl group, a trimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, or an allyldimethylsilyl group.

As in formula (B), R^(X) and R^(Y) in formula (C) independently can be Hor any halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenatedhydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, or C₁ to C₃₆hydrocarbylsilyl group disclosed herein (e.g., as pertaining tosubstituents on Cp^(A) and Cp^(B) in formula (A)). In one aspect, forexample, R^(X) and R^(Y) independently can be H or a C₁ to C₁₂hydrocarbyl group. In another aspect, R^(X) and R^(Y) independently canbe a C₁ to C₁₀ hydrocarbyl group. In yet another aspect, R^(X) and R^(Y)independently can be H, Cl, CF₃, a methyl group, an ethyl group, apropyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexyl group,a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a tolyl group, a benzyl group, a naphthyl group,a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilylgroup, or an allyldimethylsilyl group, and the like. In still anotheraspect, R^(X) and R^(Y) independently can be a methyl group, an ethylgroup, a propyl group, a butyl group, a pentyl group, a hexyl group, aheptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a tolyl group, or a benzyl group.

As in formula (A), each X in formula (C) independently can be H, BH₄, orany halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ hydrocarboxy group,C₁ to C₃₆ hydrocarbylaminyl group, C₁ to C₃₆ hydrocarbylsilyl group, orC₁ to C₃₆ hydrocarbylaminylsilyl group disclosed herein, or —OBR¹ ₂ or—OSO₂R¹, wherein R¹ is any C₁ to C₃₆ hydrocarbyl group disclosed herein.For example, each X independently can be a halide or a C₁ to C₁₈hydrocarbyl group. In a particular aspect, each X can be Cl.

In accordance with aspects of this invention, the metal in formula (C),M³, can be Zr or Hf. In one aspect, for instance, M³ can be Zr, while inanother aspect, M³ can be Hf. The bridging atom E³ can be C, Si, or Ge,and each R³ independently can be H or any C₁ to C₁₈ hydrocarbyl groupdisclosed herein, however, at least one R³ is an aryl group having up to18 carbon atoms. In some aspects, the bridging atom E³ can be C and,additionally or alternatively, one R³ can be a phenyl group and theother R³ can be a C₁ to C₈ alkyl group or a C₃ to C₈ alkenyl group. Forexample, each R³ independently can be a methyl group, an ethyl group, apropyl group, a butyl group, a pentyl group, a hexyl group, a heptylgroup, an octyl group, a nonyl group, a decyl group, an ethenyl group, apropenyl group, a butenyl group, a pentenyl group, a hexenyl group, aheptenyl group, an octenyl group, a nonenyl group, a decenyl group, aphenyl group, a cyclohexylphenyl group, a naphthyl group, a tolyl group,or a benzyl group, wherein at least one R³ is an aryl group (e.g., aphenyl group). In certain aspects, each R³ can be a phenyl group.

Illustrative and non-limiting examples of bridged metallocene compoundshaving formula (C) and/or suitable for use as catalyst component III caninclude the following compounds (Ph=phenyl):

and the like, as well as combinations thereof.

Activator-Supports

The present invention encompasses various catalyst compositionscontaining an activator, such as activator-support. In one aspect, theactivator-support can comprise a chemically-treated solid oxide.Alternatively, in another aspect, the activator-support can comprise aclay mineral, a pillared clay, an exfoliated clay, an exfoliated claygelled into another oxide matrix, a layered silicate mineral, anon-layered silicate mineral, a layered aluminosilicate mineral, anon-layered aluminosilicate mineral, or combinations thereof.

Generally, chemically-treated solid oxides exhibit enhanced acidity ascompared to the corresponding untreated solid oxide compound. Thechemically-treated solid oxide also can function as a catalyst activatoras compared to the corresponding untreated solid oxide. While thechemically-treated solid oxide can activate a metallocene complex in theabsence of co-catalysts, it is not necessary to eliminate co-catalystsfrom the catalyst composition. The activation function of theactivator-support can enhance the activity of catalyst composition as awhole, as compared to a catalyst composition containing thecorresponding untreated solid oxide. However, it is believed that thechemically-treated solid oxide can function as an activator, even in theabsence of organoaluminum compounds, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.

The chemically-treated solid oxide can comprise a solid oxide treatedwith an electron-withdrawing anion. While not intending to be bound bythe following statement, it is believed that treatment of the solidoxide with an electron-withdrawing component augments or enhances theacidity of the oxide. Thus, either the activator-support exhibits Lewisor Brønsted acidity that is typically greater than the Lewis or Brønstedacid strength of the untreated solid oxide, or the activator-support hasa greater number of acid sites than the untreated solid oxide, or both.One method to quantify the acidity of the chemically-treated anduntreated solid oxide materials can be by comparing the polymerizationactivities of the treated and untreated oxides under acid catalyzedreactions.

Chemically-treated solid oxides of this invention generally can beformed from an inorganic solid oxide that exhibits Lewis acidic orBrønsted acidic behavior and has a relatively high porosity. The solidoxide can be chemically-treated with an electron-withdrawing component,typically an electron-withdrawing anion, to form an activator-support.

According to one aspect of the present invention, the solid oxide usedto prepare the chemically-treated solid oxide can have a pore volumegreater than about 0.1 cc/g. According to another aspect of the presentinvention, the solid oxide can have a pore volume greater than about 0.5cc/g. According to yet another aspect of the present invention, thesolid oxide can have a pore volume greater than about 1.0 cc/g.

In another aspect, the solid oxide can have a surface area of from about100 to about 1000 m²/g. In yet another aspect, the solid oxide can havea surface area of from about 200 to about 800 m²/g. In still anotheraspect of the present invention, the solid oxide can have a surface areaof from about 250 to about 600 m²/g.

The chemically-treated solid oxide can comprise a solid inorganic oxidecomprising oxygen and one or more elements selected from Group 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, orcomprising oxygen and one or more elements selected from the lanthanideor actinide elements (See: Hawley's Condensed Chemical Dictionary,11^(th) Ed., John Wiley & Sons, 1995; Cotton, F. A., Wilkinson, G.,Murillo, C. A., and Bochmann, M., Advanced Inorganic Chemistry, 6^(th)Ed., Wiley-Interscience, 1999). For example, the inorganic oxide cancomprise oxygen and an element, or elements, selected from Al, B, Be,Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V,W, P, Y, Zn, and Zr.

Suitable examples of solid oxide materials or compounds that can be usedto form the chemically-treated solid oxide can include, but are notlimited to, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO, Fe₂O₃,Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂,TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixed oxidesthereof, and combinations thereof. For example, the solid oxide cancomprise silica, alumina, silica-alumina, silica-coated alumina,aluminum phosphate, aluminophosphate, heteropolytungstate, titania,zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or anycombination thereof.

The solid oxide of this invention encompasses oxide materials such asalumina, “mixed oxides” thereof such as silica-alumina, materials whereone oxide is coated with another, as well as any combinations andmixtures thereof. The mixed oxide compounds such as silica-alumina canbe single or multiple chemical phases with more than one metal combinedwith oxygen to form a solid oxide compound. Examples of mixed oxidesthat can be used in the activator-support of the present invention,either singly or in combination, can include, but are not limited to,silica-alumina, silica-titania, silica-zirconia, zeolites, various clayminerals, alumina-titania, alumina-zirconia, zinc-aluminate,alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia,and the like. The solid oxide of this invention also encompasses oxidematerials such as silica-coated alumina, as described in U.S. Pat. No.7,884,163, the disclosure of which is incorporated herein by referencein its entirety.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspectof the present invention, the electron-withdrawing component can be anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Examples of electron-withdrawing anions caninclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, and the like, including mixtures andcombinations thereof. In addition, other ionic or non-ionic compoundsthat serve as sources for these electron-withdrawing anions also can beemployed in the present invention. It is contemplated that theelectron-withdrawing anion can be, or can comprise, fluoride, chloride,bromide, phosphate, triflate, bisulfate, or sulfate, and the like, orany combination thereof, in some aspects of this invention. In otheraspects, the electron-withdrawing anion can comprise sulfate, bisulfate,fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate,phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, or combinations thereof.

Thus, for example, the activator-support (e.g., chemically-treated solidoxide) used in the catalyst compositions of the present invention canbe, or can comprise, fluorided alumina, chlorided alumina, bromidedalumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, and the like, or combinations thereof.In one aspect, the activator-support can be, or can comprise, fluoridedalumina, sulfated alumina, fluorided silica-alumina, sulfatedsilica-alumina, fluorided silica-coated alumina, sulfated silica-coatedalumina, phosphated silica-coated alumina, and the like, or anycombination thereof. In another aspect, the activator-support cancomprise fluorided alumina; alternatively, chlorided alumina;alternatively, sulfated alumina; alternatively, fluoridedsilica-alumina; alternatively, sulfated silica-alumina; alternatively,fluorided silica-zirconia; alternatively, chlorided silica-zirconia; oralternatively, fluorided silica-coated alumina

When the electron-withdrawing component comprises a salt of anelectron-withdrawing anion, the counterion or cation of that salt can beselected from any cation that allows the salt to revert or decomposeback to the acid during calcining. Factors that dictate the suitabilityof the particular salt to serve as a source for the electron-withdrawinganion can include, but are not limited to, the solubility of the salt inthe desired solvent, the lack of adverse reactivity of the cation,ion-pairing effects between the cation and anion, hygroscopic propertiesimparted to the salt by the cation, and the like, and thermal stabilityof the anion. Examples of suitable cations in the salt of theelectron-withdrawing anion can include, but are not limited to,ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkylphosphonium, H⁺, [H(OEt₂)₂]⁺, and the like.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the activator-support to the desired level. Combinations ofelectron-withdrawing components can be contacted with the oxide materialsimultaneously or individually, and in any order that affords thedesired chemically-treated solid oxide acidity. For example, one aspectof this invention can employ two or more electron-withdrawing anionsource compounds in two or more separate contacting steps.

Thus, a process by which a chemically-treated solid oxide can beprepared is as follows: a selected solid oxide, or combination of solidoxides, can be contacted with a first electron-withdrawing anion sourcecompound to form a first mixture; this first mixture can be calcined andthen contacted with a second electron-withdrawing anion source compoundto form a second mixture; the second mixture then can be calcined toform a treated solid oxide. In such a process, the first and secondelectron-withdrawing anion source compounds can be either the same ordifferent compounds.

According to another aspect of the present invention, thechemically-treated solid oxide can comprise a solid inorganic oxidematerial, a mixed oxide material, or a combination of inorganic oxidematerials, that is chemically-treated with an electron-withdrawingcomponent, and optionally treated with a metal source, including metalsalts, metal ions, or other metal-containing compounds. Non-limitingexamples of the metal or metal ion can include zinc, nickel, vanadium,titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium,and the like, or combinations thereof. Examples of chemically-treatedsolid oxides that contain a metal or metal ion can include, but are notlimited to, chlorided zinc-impregnated alumina, fluoridedtitanium-impregnated alumina, fluorided zinc-impregnated alumina,chlorided zinc-impregnated silica-alumina, fluorided zinc-impregnatedsilica-alumina, sulfated zinc-impregnated alumina, chlorided zincaluminate, fluorided zinc aluminate, sulfated zinc aluminate,silica-coated alumina treated with hexafluorotitanic acid, silica-coatedalumina treated with zinc and then fluorided, and the like, or anycombination thereof.

Any method of impregnating the solid oxide material with a metal can beused. The method by which the oxide is contacted with a metal source,typically a salt or metal-containing compound, can include, but is notlimited to, gelling, co-gelling, impregnation of one compound ontoanother, and the like. If desired, the metal-containing compound can beadded to or impregnated into the solid oxide in solution form, andsubsequently converted into the supported metal upon calcining.Accordingly, the solid inorganic oxide can further comprise a metalselected from zinc, titanium, nickel, vanadium, silver, copper, gallium,tin, tungsten, molybdenum, and the like, or combinations of thesemetals. For example, zinc often can be used to impregnate the solidoxide because it can provide improved catalyst activity at a low cost.

The solid oxide can be treated with metal salts or metal-containingcompounds before, after, or at the same time that the solid oxide istreated with the electron-withdrawing anion. Following any contactingmethod, the contacted mixture of solid compound, electron-withdrawinganion, and the metal ion can be calcined. Alternatively, a solid oxidematerial, an electron-withdrawing anion source, and the metal salt ormetal-containing compound can be contacted and calcined simultaneously.

Various processes can be used to form the chemically-treated solid oxideuseful in the present invention. The chemically-treated solid oxide cancomprise the contact product of one or more solid oxides with one ormore electron-withdrawing anion sources. It is not required that thesolid oxide be calcined prior to contacting the electron-withdrawinganion source. Typically, the contact product can be calcined eitherduring or after the solid oxide is contacted with theelectron-withdrawing anion source. The solid oxide can be calcined oruncalcined. Various processes to prepare solid oxide activator-supportsthat can be employed in this invention have been reported. For example,such methods are described in U.S. Pat. Nos. 6,107,230, 6,165,929,6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,388,017,6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,548,442, 6,576,583,6,613,712, 6,632,894, 6,667,274, and 6,750,302, the disclosures of whichare incorporated herein by reference in their entirety.

According to one aspect of the present invention, the solid oxidematerial can be chemically-treated by contacting it with anelectron-withdrawing component, typically an electron-withdrawing anionsource. Further, the solid oxide material optionally can be chemicallytreated with a metal ion, and then calcined to form a metal-containingor metal-impregnated chemically-treated solid oxide. According toanother aspect of the present invention, the solid oxide material andelectron-withdrawing anion source can be contacted and calcinedsimultaneously.

The method by which the oxide is contacted with the electron-withdrawingcomponent, typically a salt or an acid of an electron-withdrawing anion,can include, but is not limited to, gelling, co-gelling, impregnation ofone compound onto another, and the like. Thus, following any contactingmethod, the contacted mixture of the solid oxide, electron-withdrawinganion, and optional metal ion, can be calcined.

The solid oxide activator-support (i.e., chemically-treated solid oxide)thus can be produced by a process comprising:

1) contacting a solid oxide (or solid oxides) with anelectron-withdrawing anion source compound (or compounds) to form afirst mixture; and

2) calcining the first mixture to form the solid oxideactivator-support.

According to another aspect of the present invention, the solid oxideactivator-support (chemically-treated solid oxide) can be produced by aprocess comprising:

1) contacting a solid oxide (or solid oxides) with a firstelectron-withdrawing anion source compound to form a first mixture;

2) calcining the first mixture to produce a calcined first mixture;

3) contacting the calcined first mixture with a secondelectron-withdrawing anion source compound to form a second mixture; and

4) calcining the second mixture to form the solid oxideactivator-support.

According to yet another aspect of the present invention, thechemically-treated solid oxide can be produced or formed by contactingthe solid oxide with the electron-withdrawing anion source compound,where the solid oxide compound is calcined before, during, or aftercontacting the electron-withdrawing anion source, and where there is asubstantial absence of aluminoxanes, organoboron or organoboratecompounds, and ionizing ionic compounds.

Calcining of the treated solid oxide generally can be conducted in anambient atmosphere, typically in a dry ambient atmosphere, at atemperature from about 200° C. to about 900° C., and for a time of about1 minute to about 100 hours. Calcining can be conducted at a temperatureof from about 300° C. to about 800° C., or alternatively, at atemperature of from about 400° C. to about 700° C. Calcining can beconducted for about 30 minutes to about 50 hours, or for about 1 hour toabout 15 hours. Thus, for example, calcining can be carried out forabout 1 to about 10 hours at a temperature of from about 350° C. toabout 550° C. Any suitable ambient atmosphere can be employed duringcalcining. Generally, calcining can be conducted in an oxidizingatmosphere, such as air. Alternatively, an inert atmosphere, such asnitrogen or argon, or a reducing atmosphere, such as hydrogen or carbonmonoxide, can be used.

According to one aspect of the present invention, the solid oxidematerial can be treated with a source of halide ion, sulfate ion, or acombination of anions, optionally treated with a metal ion, and thencalcined to provide the chemically-treated solid oxide in the form of aparticulate solid. For example, the solid oxide material can be treatedwith a source of sulfate (termed a “sulfating agent”), a source ofbromide ion (termed a “bromiding agent”), a source of chloride ion(termed a “chloriding agent”), a source of fluoride ion (termed a“fluoriding agent”), or a combination thereof, and calcined to providethe solid oxide activator. Useful acidic activator-supports can include,but are not limited to, bromided alumina, chlorided alumina, fluoridedalumina, sulfated alumina, bromided silica-alumina, chloridedsilica-alumina, fluorided silica-alumina, sulfated silica-alumina,bromided silica-zirconia, chlorided silica-zirconia, fluoridedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,alumina treated with hexafluorotitanic acid, silica-coated aluminatreated with hexafluorotitanic acid, silica-alumina treated withhexafluorozirconic acid, silica-alumina treated with trifluoroaceticacid, fluorided boria-alumina, silica treated with tetrafluoroboricacid, alumina treated with tetrafluoroboric acid, alumina treated withhexafluorophosphoric acid, a pillared clay, such as a pillaredmontmorillonite, optionally treated with fluoride, chloride, or sulfate;phosphated alumina or other aluminophosphates optionally treated withsulfate, fluoride, or chloride; or any combination of the above.Further, any of these activator-supports optionally can be treated orimpregnated with a metal ion.

In an aspect, the chemically-treated solid oxide can comprise afluorided solid oxide in the form of a particulate solid. The fluoridedsolid oxide can be formed by contacting a solid oxide with a fluoridingagent. The fluoride ion can be added to the oxide by forming a slurry ofthe oxide in a suitable solvent such as alcohol or water including, butnot limited to, the one to three carbon alcohols because of theirvolatility and low surface tension. Examples of suitable fluoridingagents can include, but are not limited to, hydrofluoric acid (HF),ammonium fluoride (NH₄F), ammonium bifluoride (NH₄HF₂), ammoniumtetrafluoroborate (NH₄BF₄), ammonium silicofluoride (hexafluorosilicate)((NH₄)₂SiF₆), ammonium hexafluorophosphate (NH₄ PF₆), hexafluorotitanicacid (H₂TiF₆), ammonium hexafluorotitanic acid ((NH₄)₂TiF₆),hexafluorozirconic acid (H₂ZrF₆), AlF₃, NH₄AlF₄, analogs thereof, andcombinations thereof. Triflic acid and ammonium triflate also can beemployed. For example, ammonium bifluoride (NH₄HF₂) can be used as thefluoriding agent, due to its ease of use and availability.

If desired, the solid oxide can be treated with a fluoriding agentduring the calcining step. Any fluoriding agent capable of thoroughlycontacting the solid oxide during the calcining step can be used. Forexample, in addition to those fluoriding agents described previously,volatile organic fluoriding agents can be used. Examples of volatileorganic fluoriding agents useful in this aspect of the invention caninclude, but are not limited to, freons, perfluorohexane,perfluorobenzene, fluoromethane, trifluoroethanol, and the like, andcombinations thereof. Calcining temperatures generally must be highenough to decompose the compound and release fluoride. Gaseous hydrogenfluoride (HF) or fluorine (F₂) itself also can be used with the solidoxide if fluorided while calcining. Silicon tetrafluoride (SiF₄) andcompounds containing tetrafluoroborate (BF₄ ⁻) also can be employed. Oneconvenient method of contacting the solid oxide with the fluoridingagent can be to vaporize a fluoriding agent into a gas stream used tofluidize the solid oxide during calcination.

Similarly, in another aspect of this invention, the chemically-treatedsolid oxide can comprise a chlorided solid oxide in the form of aparticulate solid. The chlorided solid oxide can be formed by contactinga solid oxide with a chloriding agent. The chloride ion can be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Thesolid oxide can be treated with a chloriding agent during the calciningstep. Any chloriding agent capable of serving as a source of chlorideand thoroughly contacting the oxide during the calcining step can beused, such as SiCl₄, SiMe₂Cl₂, TiCl₄, BCl₃, and the like, includingmixtures thereof. Volatile organic chloriding agents can be used.Examples of suitable volatile organic chloriding agents can include, butare not limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, andthe like, or any combination thereof. Gaseous hydrogen chloride orchlorine itself also can be used with the solid oxide during calcining.One convenient method of contacting the oxide with the chloriding agentcan be to vaporize a chloriding agent into a gas stream used to fluidizethe solid oxide during calcination.

The amount of fluoride or chloride ion present before calcining thesolid oxide generally can be from about 1 to about 50% by weight, wherethe weight percent is based on the weight of the solid oxide, forexample, silica-alumina, before calcining

According to another aspect of this invention, the amount of fluoride orchloride ion present before calcining the solid oxide can be from about1 to about 25% by weight, and according to another aspect of thisinvention, from about 2 to about 20% by weight. According to yet anotheraspect of this invention, the amount of fluoride or chloride ion presentbefore calcining the solid oxide can be from about 4 to about 10% byweight. Once impregnated with halide, the halided oxide can be dried byany suitable method including, but not limited to, suction filtrationfollowed by evaporation, drying under vacuum, spray drying, and thelike, although it is also possible to initiate the calcining stepimmediately without drying the impregnated solid oxide.

The silica-alumina used to prepare the treated silica-alumina typicallycan have a pore volume greater than about 0.5 cc/g. According to oneaspect of the present invention, the pore volume can be greater thanabout 0.8 cc/g, and according to another aspect of the presentinvention, greater than about 1.0 cc/g. Further, the silica-aluminagenerally can have a surface area greater than about 100 m²/g. Accordingto another aspect of this invention, the surface area can be greaterthan about 250 m²/g. Yet, in another aspect, the surface area can begreater than about 350 m²/g.

The silica-alumina utilized in the present invention typically can havean alumina content from about 5 to about 95% by weight. According to oneaspect of this invention, the alumina content of the silica-alumina canbe from about 5 to about 50%, or from about 8% to about 30%, alumina byweight. In another aspect, high alumina content silica-alumina compoundscan be employed, in which the alumina content of these silica-aluminacompounds typically ranges from about 60% to about 90%, or from about65% to about 80%, alumina by weight. According to yet another aspect ofthis invention, the solid oxide component can comprise alumina withoutsilica, and according to another aspect of this invention, the solidoxide component can comprise silica without alumina

The sulfated solid oxide can comprise sulfate and a solid oxidecomponent, such as alumina or silica-alumina, in the form of aparticulate solid. Optionally, the sulfated oxide can be treated furtherwith a metal ion such that the calcined sulfated oxide comprises ametal. According to one aspect of the present invention, the sulfatedsolid oxide can comprise sulfate and alumina. In some instances, thesulfated alumina can be formed by a process wherein the alumina istreated with a sulfate source, for example, sulfuric acid or a sulfatesalt such as ammonium sulfate. This process generally can be performedby forming a slurry of the alumina in a suitable solvent, such asalcohol or water, in which the desired concentration of the sulfatingagent has been added. Suitable organic solvents can include, but are notlimited to, the one to three carbon alcohols because of their volatilityand low surface tension.

According to one aspect of this invention, the amount of sulfate ionpresent before calcining can be from about 0.5 to about 100 parts byweight sulfate ion to about 100 parts by weight solid oxide. Accordingto another aspect of this invention, the amount of sulfate ion presentbefore calcining can be from about 1 to about 50 parts by weight sulfateion to about 100 parts by weight solid oxide, and according to stillanother aspect of this invention, from about 5 to about 30 parts byweight sulfate ion to about 100 parts by weight solid oxide. Theseweight ratios are based on the weight of the solid oxide beforecalcining Once impregnated with sulfate, the sulfated oxide can be driedby any suitable method including, but not limited to, suction filtrationfollowed by evaporation, drying under vacuum, spray drying, and thelike, although it is also possible to initiate the calcining stepimmediately.

According to another aspect of the present invention, theactivator-support used in preparing the catalyst compositions of thisinvention can comprise an ion-exchangeable activator-support including,but not limited to, silicate and aluminosilicate compounds or minerals,either with layered or non-layered structures, and combinations thereof.In another aspect of this invention, ion-exchangeable, layeredaluminosilicates such as pillared clays can be used asactivator-supports. When the acidic activator-support comprises anion-exchangeable activator-support, it can optionally be treated with atleast one electron-withdrawing anion such as those disclosed herein,though typically the ion-exchangeable activator-support is not treatedwith an electron-withdrawing anion.

According to another aspect of the present invention, theactivator-support of this invention can comprise clay minerals havingexchangeable cations and layers capable of expanding. Typical claymineral activator-supports can include, but are not limited to,ion-exchangeable, layered aluminosilicates such as pillared clays.Although the term “support” is used, it is not meant to be construed asan inert component of the catalyst composition, but rather can beconsidered an active part of the catalyst composition, because of itsintimate association with the metallocene component.

According to another aspect of the present invention, the clay materialsof this invention can encompass materials either in their natural stateor that have been treated with various ions by wetting, ion exchange, orpillaring. Typically, the clay material activator-support of thisinvention can comprise clays that have been ion exchanged with largecations, including polynuclear, highly charged metal complex cations.However, the clay material activator-supports of this invention also canencompass clays that have been ion exchanged with simple salts,including, but not limited to, salts of Al(III), Fe(II), Fe(III), andZn(II) with ligands such as halide, acetate, sulfate, nitrate, ornitrite.

According to another aspect of the present invention, theactivator-support can comprise a pillared clay. The term “pillared clay”is used to refer to clay materials that have been ion exchanged withlarge, typically polynuclear, highly charged metal complex cations.Examples of such ions can include, but are not limited to, Keggin ionswhich can have charges such as 7+, various polyoxometallates, and otherlarge ions. Thus, the term pillaring can refer to a simple exchangereaction in which the exchangeable cations of a clay material arereplaced with large, highly charged ions, such as Keggin ions. Thesepolymeric cations then can be immobilized within the interlayers of theclay and when calcined are converted to metal oxide “pillars,”effectively supporting the clay layers as column-like structures. Thus,once the clay is dried and calcined to produce the supporting pillarsbetween clay layers, the expanded lattice structure can be maintainedand the porosity can be enhanced. The resulting pores can vary in shapeand size as a function of the pillaring material and the parent claymaterial used. Examples of pillaring and pillared clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J. M. Thomas,Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3,pp. 55-99, Academic Press, Inc., (1972); U.S. Pat. No. 4,452,910; U.S.Pat. No. 5,376,611; and U.S. Pat. No. 4,060,480; the disclosures ofwhich are incorporated herein by reference in their entirety.

The pillaring process can utilize clay minerals having exchangeablecations and layers capable of expanding. Any pillared clay that canenhance the polymerization of olefins in the catalyst composition of thepresent invention can be used. Therefore, suitable clay minerals forpillaring can include, but are not limited to, allophanes; smectites,both dioctahedral (A1) and tri-octahedral (Mg) and derivatives thereofsuch as montmorillonites (bentonites), nontronites, hectorites, orlaponites; halloysites; vermiculites; micas; fluoromicas; chlorites;mixed-layer clays; the fibrous clays including but not limited tosepiolites, attapulgites, and palygorskites; a serpentine clay; illite;laponite; saponite; and any combination thereof. In one aspect, thepillared clay activator-support can comprise bentonite ormontmorillonite. The principal component of bentonite ismontmorillonite.

The pillared clay can be pretreated if desired. For example, a pillaredbentonite can be pretreated by drying at about 300° C. under an inertatmosphere, typically dry nitrogen, for about 3 hours, before beingadded to the polymerization reactor. Although an exemplary pretreatmentis described herein, it should be understood that the preheating can becarried out at many other temperatures and times, including anycombination of temperature and time steps, all of which are encompassedby this invention.

The activator-support used to prepare the catalyst compositions of thepresent invention can be combined with other inorganic supportmaterials, including, but not limited to, zeolites, inorganic oxides,phosphated inorganic oxides, and the like. In one aspect, typicalsupport materials that can be used include, but are not limited to,silica, silica-alumina, alumina, titania, zirconia, magnesia, boria,thoria, aluminophosphate, aluminum phosphate, silica-titania,coprecipitated silica/titania, mixtures thereof, or any combinationthereof.

According to another aspect of the present invention, one or more of themetallocene compounds can be precontacted with an olefin monomer and anorganoaluminum compound for a first period of time prior to contactingthis mixture with the activator-support. Once the precontacted mixtureof metallocene complex(es), olefin monomer, and organoaluminum compoundis contacted with the activator-support, the composition furthercomprising the activator-support can be termed a “postcontacted”mixture. The postcontacted mixture can be allowed to remain in furthercontact for a second period of time prior to being charged into thereactor in which the polymerization process will be carried out.

According to yet another aspect of the present invention, one or more ofthe metallocene compounds can be precontacted with an olefin monomer andan activator-support for a first period of time prior to contacting thismixture with the organoaluminum compound. Once the precontacted mixtureof the metallocene complex(es), olefin monomer, and activator-support iscontacted with the organoaluminum compound, the composition furthercomprising the organoaluminum can be termed a “postcontacted” mixture.The postcontacted mixture can be allowed to remain in further contactfor a second period of time prior to being introduced into thepolymerization reactor.

Co-Catalysts

In certain aspects directed to catalyst compositions containing aco-catalyst, the co-catalyst can comprise a metal hydrocarbyl compound,examples of which include non-halide metal hydrocarbyl compounds, metalhydrocarbyl halide compounds, non-halide metal alkyl compounds, metalalkyl halide compounds, and so forth. The hydrocarbyl group (or alkylgroup) can be any hydrocarbyl (or alkyl) group disclosed herein.Moreover, in some aspects, the metal of the metal hydrocarbyl can be agroup 1, 2, 11, 12, 13, or 14 metal; alternatively, a group 13 or 14metal; or alternatively, a group 13 metal. Hence, in some aspects, themetal of the metal hydrocarbyl (non-halide metal hydrocarbyl or metalhydrocarbyl halide) can be lithium, sodium, potassium, rubidium, cesium,beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron,aluminum, or tin; alternatively, lithium, sodium, potassium, magnesium,calcium, zinc, boron, aluminum, or tin; alternatively, lithium, sodium,or potassium; alternatively, magnesium or calcium; alternatively,lithium; alternatively, sodium; alternatively, potassium; alternatively,magnesium; alternatively, calcium; alternatively, zinc; alternatively,boron; alternatively, aluminum; or alternatively, tin. In some aspects,the metal hydrocarbyl or metal alkyl, with or without a halide, cancomprise a lithium hydrocarbyl or alkyl, a magnesium hydrocarbyl oralkyl, a boron hydrocarbyl or alkyl, a zinc hydrocarbyl or alkyl, or analuminum hydrocarbyl or alkyl.

In particular aspects directed to catalyst compositions containing aco-catalyst (e.g., the activator can comprise a solid oxide treated withan electron-withdrawing anion), the co-catalyst can comprise analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, an organoaluminum compound, an organozinccompound, an organomagnesium compound, or an organolithium compound, andthis includes any combinations of these materials. In one aspect, theco-catalyst can comprise an organoaluminum compound. In another aspect,the co-catalyst can comprise an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, an organozinccompound, an organomagnesium compound, an organolithium compound, or anycombination thereof. In yet another aspect, the co-catalyst can comprisean aluminoxane compound; alternatively, an organoboron or organoboratecompound; alternatively, an ionizing ionic compound; alternatively, anorganozinc compound; alternatively, an organomagnesium compound; oralternatively, an organolithium compound.

Organoaluminum Compounds

In some aspects, catalyst compositions of the present invention cancomprise one or more organoaluminum compounds. Such compounds caninclude, but are not limited to, compounds having the formula:

(R^(Z))₃Al;

where each Rz independently can be an aliphatic group having from 1 to10 carbon atoms. For example, each Rz independently can be methyl,ethyl, propyl, butyl, hexyl, or isobutyl.

Other organoaluminum compounds which can be used in catalystcompositions disclosed herein can include, but are not limited to,compounds having the formula:

Al(X⁷)_(m)(X⁸)_(3-m),

where each X⁷ independently can be a hydrocarbyl; each X⁸ independentlycan be an alkoxide or an aryloxide, a halide, or a hydride; and m can befrom 1 to 3, inclusive. Hydrocarbyl is used herein to specify ahydrocarbon radical group and includes, for instance, aryl, alkyl,cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl,aralkenyl, and aralkenyl groups.

In one aspect, each X⁷ independently can be any hydrocarbyl having from1 to about 18 carbon atoms disclosed herein. In another aspect of thepresent invention, each X⁷ independently can be any alkyl having from 1to 10 carbon atoms disclosed herein. For example, each X⁷ independentlycan be methyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl, or hexyl,and the like, in yet another aspect of the present invention.

According to one aspect of the present invention, each X⁸ independentlycan be an alkoxide or an aryloxide, any one of which has from 1 to 18carbon atoms, a halide, or a hydride. In another aspect of the presentinvention, each X⁸ can be selected independently from fluorine andchlorine. Yet, in another aspect, X⁸ can be chlorine.

In the formula, Al(X⁷)_(m)(X⁸)_(3-m), m can be a number from 1 to 3,inclusive, and typically, m can be 3. The value of m is not restrictedto be an integer; therefore, this formula can include sesquihalidecompounds or other organoaluminum cluster compounds.

Examples of organoaluminum compounds suitable for use in accordance withthe present invention can include, but are not limited to,trialkylaluminum compounds, dialkylaluminum halide compounds,dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds,and combinations thereof. Specific non-limiting examples of suitableorganoaluminum compounds can include trimethylaluminum (TMA),triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum(TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, and the like, or combinationsthereof.

The present invention contemplates a method of precontacting ametallocene compound (or compounds) with an organoaluminum compound andan olefin monomer to form a precontacted mixture, prior to contactingthis precontacted mixture with an activator-support to form a catalystcomposition. When the catalyst composition is prepared in this manner,typically, though not necessarily, a portion of the organoaluminumcompound can be added to the precontacted mixture and another portion ofthe organoaluminum compound can be added to the postcontacted mixtureprepared when the precontacted mixture is contacted with the solid oxideactivator-support. However, the entire organoaluminum compound can beused to prepare the catalyst composition in either the precontacting orpostcontacting step. Alternatively, all the catalyst components can becontacted in a single step.

Further, more than one organoaluminum compound can be used in either theprecontacting or the postcontacting step. When an organoaluminumcompound is added in multiple steps, the amounts of organoaluminumcompound disclosed herein include the total amount of organoaluminumcompound used in both the precontacted and postcontacted mixtures, andany additional organoaluminum compound added to the polymerizationreactor. Therefore, total amounts of organoaluminum compounds aredisclosed regardless of whether a single organoaluminum compound or morethan one organoaluminum compound is used.

Aluminoxane Compounds

Certain aspects of the present invention provide a catalyst compositionwhich can comprise an aluminoxane compound. As used herein, the terms“aluminoxane” and “aluminoxane compound” refer to aluminoxane compounds,compositions, mixtures, or discrete species, regardless of how suchaluminoxanes are prepared, formed or otherwise provided. For example, acatalyst composition comprising an aluminoxane compound can be preparedin which aluminoxane is provided as the poly(hydrocarbyl aluminumoxide), or in which aluminoxane is provided as the combination of analuminum alkyl compound and a source of active protons such as water.Aluminoxanes also can be referred to as poly(hydrocarbyl aluminumoxides) or organoaluminoxanes.

The other catalyst components typically can be contacted with thealuminoxane in a saturated hydrocarbon compound solvent, though anysolvent that is substantially inert to the reactants, intermediates, andproducts of the activation step can be used. The catalyst compositionformed in this manner can be collected by any suitable method, forexample, by filtration. Alternatively, the catalyst composition can beintroduced into the polymerization reactor without being isolated.

The aluminoxane compound of this invention can be an oligomeric aluminumcompound comprising linear structures, cyclic structures, or cagestructures, or mixtures of all three. Cyclic aluminoxane compoundshaving the formula:

wherein each R in this formula independently can be a linear or branchedalkyl having from 1 to 10 carbon atoms, and p in this formula can be aninteger from 3 to 20, are encompassed by this invention. The AlRO moietyshown here also can constitute the repeating unit in a linearaluminoxane. Thus, linear aluminoxanes having the formula:

wherein each R in this formula independently can be a linear or branchedalkyl having from 1 to 10 carbon atoms, and q in this formula can be aninteger from 1 to 50, are also encompassed by this invention.

Further, aluminoxanes can have cage structures of the formula R^(t)_(5r+α)R^(b) _(r-α)Al_(4r)O_(3r), wherein each R^(t) independently canbe a terminal linear or branched alkyl group having from 1 to 10 carbonatoms; each Rb independently can be a bridging linear or branched alkylgroup having from 1 to 10 carbon atoms; r can be 3 or 4; and a can beequal to n_(A1(3))−n_(O(2))+n_(O(4)), wherein n_(A1(3)) is the number ofthree coordinate aluminum atoms, n_(O(2)) is the number of twocoordinate oxygen atoms, and n_(O(4)) is the number of 4 coordinateoxygen atoms.

Thus, aluminoxanes which can be employed in the catalyst compositions ofthe present invention can be represented generally by formulas such as(R-Al—O)_(p), R(R-Al—O)_(q)AlR₂, and the like. In these formulas, each Rgroup independently can be a linear or branched C₁-C₆ alkyl, such asmethyl, ethyl, propyl, butyl, pentyl, or hexyl. Examples of aluminoxanecompounds that can be used in accordance with the present invention caninclude, but are not limited to, methylaluminoxane, modifiedmethylaluminoxane, ethylaluminoxane, n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane,neopentylaluminoxane, and the like, or any combination thereof.Methylaluminoxane, ethylaluminoxane, and iso-butylaluminoxane can beprepared from trimethylaluminum, triethylaluminum, ortriisobutylaluminum, respectively, and sometimes are referred to aspoly(methyl aluminum oxide), poly(ethyl aluminum oxide), andpoly(isobutyl aluminum oxide), respectively. It is also within the scopeof the invention to use an aluminoxane in combination with atrialkylaluminum, such as that disclosed in U.S. Pat. No. 4,794,096,incorporated herein by reference in its entirety.

The present invention contemplates many values of p and q in thealuminoxane formulas (R-Al—O)_(p) and R(R-Al—O)_(q)AlR₂, respectively.In some aspects, p and q can be at least 3. However, depending upon howthe organoaluminoxane is prepared, stored, and used, the value of p andq can vary within a single sample of aluminoxane, and such combinationsof organoaluminoxanes are contemplated herein.

In preparing a catalyst composition containing an aluminoxane, the molarratio of the total moles of aluminum in the aluminoxane (oraluminoxanes) to the total moles of metallocene complex(es) in thecomposition generally can be between about 1:10 and about 100,000:1. Inanother aspect, the molar ratio can be in a range from about 5:1 toabout 15,000:1. Optionally, aluminoxane can be added to a polymerizationzone in ranges from about 0.01 mg/L to about 1000 mg/L, from about 0.1mg/L to about 100 mg/L, or from about 1 mg/L to about 50 mg/L.

Organoaluminoxanes can be prepared by various procedures. Examples oforganoaluminoxane preparations are disclosed in U.S. Pat. Nos. 3,242,099and 4,808,561, the disclosures of which are incorporated herein byreference in their entirety. For example, water in an inert organicsolvent can be reacted with an aluminum alkyl compound, such as(R^(Z))₃Al, to form the desired organoaluminoxane compound. While notintending to be bound by this statement, it is believed that thissynthetic method can afford a mixture of both linear and cyclic R-Al—Oaluminoxane species, both of which are encompassed by this invention.Alternatively, organoaluminoxanes can be prepared by reacting analuminum alkyl compound, such as (R_(Z))₃Al, with a hydrated salt, suchas hydrated copper sulfate, in an inert organic solvent.

Organoboron & Organoborate Compounds

According to another aspect of the present invention, the catalystcomposition can comprise an organoboron or organoborate compound. Suchcompounds can include neutral boron compounds, borate salts, and thelike, or combinations thereof. For example, fluoroorgano boron compoundsand fluoroorgano borate compounds are contemplated.

Any fluoroorgano boron or fluoroorgano borate compound can be utilizedwith the present invention. Examples of fluoroorgano borate compoundsthat can be used in the present invention can include, but are notlimited to, fluorinated aryl borates such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like, ormixtures thereof. Examples of fluoroorgano boron compounds that can beused as co-catalysts in the present invention can include, but are notlimited to, tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, or mixturesthereof. Although not intending to be bound by the following theory,these examples of fluoroorgano borate and fluoroorgano boron compounds,and related compounds, can form “weakly-coordinating” anions whencombined with a transition metal complex (see e.g., U.S. Pat. No.5,919,983, the disclosure of which is incorporated herein by referencein its entirety). Applicants also contemplate the use of diboron, orbis-boron, compounds or other bifunctional compounds containing two ormore boron atoms in the chemical structure, such as disclosed in J. Am.Chem. Soc., 2005, 127, pp. 14756-14768, the content of which isincorporated herein by reference in its entirety.

Generally, any amount of organoboron compound can be used. According toone aspect of this invention, the molar ratio of the total moles oforganoboron or organoborate compound (or compounds) to the total molesof metallocene compounds in the catalyst composition can be in a rangefrom about 0.1:1 to about 15:1. Typically, the amount of thefluoroorgano boron or fluoroorgano borate compound used can be fromabout 0.5 moles to about 10 moles of boron/borate compound per mole ofmetallocene complexes. According to another aspect of this invention,the amount of fluoroorgano boron or fluoroorgano borate compound can befrom about 0.8 moles to about 5 moles of boron/borate compound per moleof metallocene complexes.

Ionizing Ionic Compounds

In another aspect, catalyst compositions disclosed herein can comprisean ionizing ionic compound. An ionizing ionic compound is an ioniccompound that can function as a co-catalyst to enhance the activity ofthe catalyst composition. While not intending to be bound by theory, itis believed that the ionizing ionic compound can be capable of reactingwith a metallocene complex and converting the metallocene complex intoone or more cationic metallocene complexes, or incipient cationicmetallocene complexes. Again, while not intending to be bound by theory,it is believed that the ionizing ionic compound can function as anionizing compound by completely or partially extracting an anionicligand, such as monoanionic ligand X, from the metallocene complex.However, the ionizing ionic compound can be a co-catalyst regardless ofwhether it is ionizes the metallocene compound, abstracts a X ligand ina fashion as to form an ion pair, weakens the metal-X bond in themetallocene, simply coordinates to a X ligand, or activates themetallocene by some other mechanism.

Further, it is not necessary that the ionizing ionic compound activatethe metallocene compound only. The activation function of the ionizingionic compound can be evident in the enhanced activity of catalystcomposition as a whole, as compared to a catalyst composition that doesnot contain an ionizing ionic compound.

Examples of ionizing ionic compounds can include, but are not limitedto, the following compounds: tri(n-butyl)ammoniumtetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate,tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)_(b) orate,tri(n-butyl)ammonium tetrakis [3,5-bis(trifluoromethyl)phenyl]borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylaniliniumtetrakis(m-tolyl)borate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-dimethyl-phenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate,triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate,triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate,triphenylcarbenium tetrakis [3,5-bis(trifluoromethyl)phenyl]borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropyliumtetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropylium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl) borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassiumtetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate,and the like, or combinations thereof. Ionizing ionic compounds usefulin this invention are not limited to these; other examples of ionizingionic compounds are disclosed in U.S. Pat. Nos. 5,576,259 and 5,807,938,the disclosures of which are incorporated herein by reference in theirentirety.

Organozinc, Organomagnesium, & Organolithium Compounds

Other aspects are directed to catalyst compositions which can include anorganozinc compound, an organomagnesium compound, an organolithiumcompound, or a combination thereof. In some aspects, these compoundshave the following general formulas:

Zn(X¹⁰)(X¹¹);

Mg(X¹²)(X¹³); and

Li(X¹⁴).

In these formulas, X¹⁰, X¹², and X¹⁴ independently can be a C₁ to C₁₈hydrocarbyl group, and X¹¹ and X¹³ independently can be H, a halide, ora C₁ to C₁₈ hydrocarbyl or C₁ to C₁₈ hydrocarboxy group. It iscontemplated X¹⁰ and X¹¹ (or X¹² and X¹³) can be the same, or that X¹⁰and X¹¹ (or X¹² and X¹³) can be different.

In one aspect, X¹⁰; X¹¹, X¹², X¹³, and X¹⁴ independently can be any C₁to C₁₈ hydrocarbyl group, C₁ to C₁₂ hydrocarbyl group, C₁ to C₈hydrocarbyl group, or C₁ to C₅ hydrocarbyl group disclosed herein. Inanother aspect, X¹⁰, X¹¹, X¹², X¹³, and X¹⁴ independently can be any C₁to C₁₈ alkyl group, C₂ to C₁₈ alkenyl group, C₆ to C₁₈ aryl group, or C₇to C₁₈ aralkyl group disclosed herein; alternatively, any C₁ to C₁₂alkyl group, C₂ to C₁₂ alkenyl group, C₆ to C₁₂ aryl group, or C₇ to C₁₂aralkyl group disclosed herein; or alternatively, any C₁ to C₅ alkylgroup, C₂ to C₅ alkenyl group, C₆ to C₈ aryl group, or C₇ to C₈ aralkylgroup disclosed herein. Thus, X¹⁰, X¹¹, X¹², X¹³, and X¹⁴ independentlycan be a methyl group, an ethyl group, a propyl group, a butyl group, apentyl group, a hexyl group, a heptyl group, an octyl group, a nonylgroup, a decyl group, a undecyl group, a dodecyl group, a tridecylgroup, a tetradecyl group, a pentadecyl group, a hexadecyl group, aheptadecyl group, an octadecyl group, an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, a hexenyl group, a heptenylgroup, an octenyl group, a nonenyl group, a decenyl group, a undecenylgroup, a dodecenyl group, a tridecenyl group, a tetradecenyl group, apentadecenyl group, a hexadecenyl group, a heptadecenyl group, anoctadecenyl group, a phenyl group, a naphthyl group, a benzyl group, ora tolyl group, and the like. In yet another aspect, X¹⁰, X¹¹, X¹², X¹³,and X¹⁴ independently can be methyl, ethyl, propyl, butyl, or pentyl(e.g., neopentyl), or both X¹⁰ and X¹¹ (or both X¹² and X¹³) can bemethyl, or ethyl, or propyl, or butyl, or pentyl (e.g., neopentyl).

X¹¹ and X¹³ independently can be H, a halide, or a C₁ to C₁₈ hydrocarbylor C₁ to C₁₈ hydrocarboxy group (e.g., any C₁ to C₁₈, C₁ to C₁₂, C₁ toC₁₀, or C₁ to C₈ hydrocarboxy group disclosed herein). In some aspects,X¹¹ and X¹³ independently can be H, a halide (e.g., Cl), or a C₁ to C₁₈hydrocarbyl or C₁ to C₁₈ hydrocarboxy group; alternatively, H, a halide,or a C₁ to C₈ hydrocarbyl or C₁ to C₈ hydrocarboxy group; oralternatively, H, Br, Cl, F, I, methyl, ethyl, propyl, butyl, pentyl(e.g., neopentyl), hexyl, heptyl, octyl, nonyl, decyl, ethenyl,propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl,decenyl, phenyl, benzyl, tolyl, methoxy, ethoxy, propoxy, butoxy,pentoxy, phenoxy, toloxy, xyloxy, or benzoxy.

In other aspects, the organozinc and/or the organomagnesium compound canhave one or two hydrocarbylsilyl moieties. Each hydrocarbyl of thehydrocarbylsilyl group can be any hydrocarbyl group disclosed herein(e.g., a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenyl group, a C₆ to C₁₈aryl group, a C₇ to C₁₈ aralkyl group, etc.). Illustrative andnon-limiting examples of hydrocarbylsilyl groups can include, but arenot limited to, trimethylsilyl, triethylsilyl, tripropylsilyl (e.g.,triisopropylsilyl), tributylsilyl, tripentylsilyl, triphenylsilyl,allyldimethylsilyl, trimethylsilylmethyl, and the like.

Exemplary organozinc compounds which can be used as co-catalysts caninclude, but are not limited to, dimethylzinc, diethylzinc,dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc,di(triethylsilyl)zinc, di(triisopropylsilyl)zinc,di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc,di(trimethylsilylmethyl)zinc, and the like, or combinations thereof.

Similarly, exemplary organomagnesium compounds can include, but are notlimited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium,dibutylmagnesium, dineopentylmagnesium,di(trimethylsilylmethyl)magnesium, methylmagnesium chloride,ethylmagnesium chloride, propylmagnesium chloride, butylmagnesiumchloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesiumchloride, methylmagnesium bromide, ethylmagnesium bromide,propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesiumbromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide,ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide,neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide,methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesiumethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide,trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide,ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesiumpropoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesiumpropoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide,propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesiumphenoxide, trimethylsilylmethylmagnesium phenoxide, and the like, or anycombinations thereof.

Likewise, exemplary organolithium compounds can include, but are notlimited to, methyllithium, ethyllithium, propyllithium, butyllithium(e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium,phenyllithium, tolyllithium, xylyllithium, benzyllithium,(dimethylphenyl)methyllithium, allyllithium, and the like, orcombinations thereof.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically can includeolefin compounds having from 2 to 30 carbon atoms per molecule andhaving at least one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally can contain a major amount of ethylene (>50 molepercent) and a minor amount of comonomer (<50 mole percent), though thisis not a requirement. Comonomers that can be copolymerized with ethyleneoften can have from 3 to 20 carbon atoms in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention can include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes (e.g., 1-octene), the four normal nonenes, thefive normal decenes, and the like, or mixtures of two or more of thesecompounds. Cyclic and bicyclic olefins, including but not limited to,cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like,also can be polymerized as described above. Styrene can also be employedas a monomer in the present invention. In an aspect, the olefin monomercan comprise a C₂-C₁₀ olefin; alternatively, the olefin monomer cancomprise ethylene; or alternatively, the olefin monomer can comprisepropylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer can comprise, for example, ethylene or propylene, which iscopolymerized with at least one comonomer. According to one aspect ofthis invention, the olefin monomer in the polymerization process cancomprise ethylene. In this aspect, examples of suitable olefincomonomers an include, but are not limited to, propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene,styrene, and the like, or combinations thereof. According to one aspectof the present invention, the comonomer can comprise 1-butene,1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combinationthereof; or alternatively, 1-butene, 1-hexene, 1-octene, or anycombination thereof.

Generally, the amount of comonomer introduced into a reactor zone toproduce a copolymer can be from about 0.01 to about 50 weight percent ofthe comonomer based on the total weight of the monomer and comonomer.According to another aspect of the present invention, the amount ofcomonomer introduced into a reactor zone can be from about 0.01 to about40 weight percent comonomer based on the total weight of the monomer andcomonomer. In still another aspect, the amount of comonomer introducedinto a reactor zone can be from about 0.1 to about 35 weight percentcomonomer based on the total weight of the monomer and comonomer. Yet,in another aspect, the amount of comonomer introduced into a reactorzone can be from about 0.5 to about 20 weight percent comonomer based onthe total weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight. According to one aspect of the present invention, at least onemonomer/reactant can be ethylene, so the polymerizations are either ahomopolymerization involving only ethylene, or copolymerizations with adifferent acyclic, cyclic, terminal, internal, linear, branched,substituted, or unsubstituted olefin. In addition, the catalystcompositions of this invention can be used in the polymerization ofdiolefin compounds including, but not limited to, 1,3-butadiene,isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Catalyst Compositions

In some aspects, the present invention employs catalyst compositionscontaining catalyst component I, catalyst component II, catalystcomponent III, and an activator (one or more than one). These catalystcompositions can be utilized to produce polyolefins—homopolymers,copolymers, and the like—for a variety of end-use applications. Catalystcomponents I, II, and III are discussed hereinabove. In aspects of thepresent invention, it is contemplated that the catalyst composition cancontain more than one catalyst component I metallocene compound and/ormore than one catalyst component II metallocene compound, and/or morethan one catalyst component III metallocene compound. Further,additional catalytic compounds—other than those specified as catalystcomponent I, II, or III—can be employed in the catalyst compositionsand/or the polymerization processes, provided that the additionalcatalytic compound(s) does not detract from the advantages disclosedherein. Additionally, more than one activator also may be utilized.

The metallocene compounds of catalyst component I are discussed above.For instance, in some aspects, catalyst component I can comprise (orconsist essentially of, or consist of) an unbridged metallocene compoundhaving formula (A). The bridged metallocene compounds of catalystcomponent II also are discussed above. For instance, in some aspects,catalyst component II can comprise (or consist essentially of, orconsist of) a metallocene compound having formula (B). Moreover, thebridged metallocene compounds of catalyst component III are discussedabove. For instance, in some aspects, catalyst component III cancomprise (or consist essentially of, or consist of) a metallocenecompound having formula (C).

Generally, catalyst compositions of the present invention comprisecatalyst component I, catalyst component II, catalyst component III, andan activator. In aspects of the invention, the activator can comprise anactivator-support (e.g., an activator-support comprising a solid oxidetreated with an electron-withdrawing anion). Activator-supports usefulin the present invention are disclosed above. Optionally, such catalystcompositions can further comprise one or more than one co-catalystcompound or compounds (suitable co-catalysts, such as organoaluminumcompounds, also are discussed above). Thus, a catalyst composition ofthis invention can comprise catalyst component I, catalyst component II,catalyst component III, an activator-support, and an organoaluminumcompound. For instance, the activator-support can comprise (or consistessentially of, or consist of) fluorided alumina, chlorided alumina,bromided alumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, and the like, or combinations thereof.Additionally, the organoaluminum compound can comprise (or consistessentially of, or consist of) trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride,diethylaluminum ethoxide, diethylaluminum chloride, and the like, orcombinations thereof. Accordingly, a catalyst composition consistentwith aspects of the invention can comprise (or consist essentially of,or consist of) an unbridged zirconium or hafnium based metallocenecompound; a bridged zirconium based metallocene compound with afluorenyl group, and with no aryl groups on the bridging group; abridged zirconium or hafnium based metallocene compound with a fluorenylgroup, and an aryl group on the bridging group; sulfated alumina (orfluorided silica-alumina, or fluorided silica-coated alumina); andtriethylaluminum (or triisobutylaluminum).

In another aspect of the present invention, a catalyst composition isprovided which comprises catalyst component I, catalyst component II,catalyst component III, an activator-support, and an organoaluminumcompound, wherein this catalyst composition is substantially free ofaluminoxanes, organoboron or organoborate compounds, ionizing ioniccompounds, and/or other similar materials; alternatively, substantiallyfree of aluminoxanes; alternatively, substantially free or organoboronor organoborate compounds; or alternatively, substantially free ofionizing ionic compounds. In these aspects, the catalyst composition hascatalyst activity, to be discussed below, in the absence of theseadditional materials. For example, a catalyst composition of the presentinvention can consist essentially of catalyst component I, catalystcomponent II, catalyst component III, an activator-support, and anorganoaluminum compound, wherein no other materials are present in thecatalyst composition which would increase/decrease the activity of thecatalyst composition by more than about 10% from the catalyst activityof the catalyst composition in the absence of said materials.

However, in other aspects of this invention, theseactivators/co-catalysts can be employed. For example, a catalystcomposition comprising catalyst component I, catalyst component II,catalyst component III, and an activator-support can further comprise anoptional co-catalyst. Suitable co-catalysts in this aspect can include,but are not limited to, aluminoxane compounds, organoboron ororganoborate compounds, ionizing ionic compounds, organoaluminumcompounds, organozinc compounds, organomagnesium compounds,organolithium compounds, and the like, or any combination thereof; oralternatively, organoaluminum compounds, organozinc compounds,organomagnesium compounds, organolithium compounds, or any combinationthereof. More than one co-catalyst can be present in the catalystcomposition.

In a different aspect, a catalyst composition is provided which does notrequire an activator-support. Such a catalyst composition can comprisecatalyst component I, catalyst component II, catalyst component III, andan activator, wherein the activator comprises an aluminoxane compound,an organoboron or organoborate compound, an ionizing ionic compound, orcombinations thereof.

In a particular aspect contemplated herein, the catalyst composition isa catalyst composition comprising an activator (one or more than one),only one catalyst component I metallocene compound, only one catalystcomponent II metallocene compound, and only one catalyst component IIImetallocene compound. In these and other aspects, the catalystcomposition can comprise an activator (e.g., an activator-supportcomprising a solid oxide treated with an electron-withdrawing anion);only one unbridged zirconium or hafnium based metallocene compound orunbridged zirconium and/or hafnium based dinuclear metallocene compound;only one bridged zirconium based metallocene compound with a fluorenylgroup, and with no aryl groups on the bridging group; and only onebridged zirconium or hafnium based metallocene compound with a fluorenylgroup, and an aryl group on the bridging group.

This invention further encompasses methods of making these catalystcompositions, such as, for example, contacting the respective catalystcomponents in any order or sequence.

Catalyst component I, catalyst component II, or catalyst component III,or any combination thereof, can be precontacted with an olefinic monomerif desired, not necessarily the olefin monomer to be polymerized, and anorganoaluminum compound for a first period of time prior to contactingthis precontacted mixture with an activator-support. The first period oftime for contact, the precontact time, between the metallocenecompound(s), the olefinic monomer, and the organoaluminum compoundtypically ranges from a time period of about 1 minute to about 24 hours,for example, from about 3 minutes to about 1 hour. Precontact times fromabout 10 minutes to about 30 minutes also can be employed.Alternatively, the precontacting process can be carried out in multiplesteps, rather than a single step, in which multiple mixtures can beprepared, each comprising a different set of catalyst components. Forexample, at least two catalyst components can be contacted forming afirst mixture, followed by contacting the first mixture with at leastone other catalyst component forming a second mixture, and so forth.

Multiple precontacting steps can be carried out in a single vessel or inmultiple vessels. Further, multiple precontacting steps can be carriedout in series (sequentially), in parallel, or a combination thereof. Forexample, a first mixture of two catalyst components can be formed in afirst vessel, a second mixture comprising the first mixture plus oneadditional catalyst component can be formed in the first vessel or in asecond vessel, which is typically placed downstream of the first vessel.

In another aspect, one or more of the catalyst components can be splitand used in different precontacting treatments. For example, part of acatalyst component can be fed into a first precontacting vessel forprecontacting with at least one other catalyst component, while theremainder of that same catalyst component can be fed into a secondprecontacting vessel for precontacting with at least one other catalystcomponent, or can be fed directly into the reactor, or a combinationthereof. The precontacting can be carried out in any suitable equipment,such as tanks, stirred mix tanks, various static mixing devices, aflask, a vessel of any type, or combinations of these apparatus.

In another aspect of this invention, the various catalyst components(for example, a catalyst component I, II, and/or III metallocene, anactivator-support, an organoaluminum co-catalyst, and optionally anunsaturated hydrocarbon) can be contacted in the polymerization reactorsimultaneously while the polymerization reaction is proceeding.Alternatively, any two or more of these catalyst components can beprecontacted in a vessel prior to entering the reaction zone. Thisprecontacting step can be continuous, in which the precontacted productcan be fed continuously to the reactor, or it can be a stepwise orbatchwise process in which a batch of precontacted product can be addedto make a catalyst composition. This precontacting step can be carriedout over a time period that can range from a few seconds to as much asseveral days, or longer. In this aspect, the continuous precontactingstep generally can last from about 1 second to about 1 hour. In anotheraspect, the continuous precontacting step can last from about 10 secondsto about 45 minutes, or from about 1 minute to about 30 minutes.

Once the precontacted mixture of catalyst component I and/or catalystcomponent II and/or catalyst component III, the olefin monomer, and theorganoaluminum co-catalyst is contacted with the activator-support, thiscomposition (with the addition of the activator-support) can be termedthe “postcontacted mixture.” The postcontacted mixture optionally canremain in contact for a second period of time, the postcontact time,prior to initiating the polymerization process. Postcontact timesbetween the precontacted mixture and the activator-support generallyrange from about 1 minute to about 24 hours. In a further aspect, thepostcontact time can be in a range from about 3 minutes to about 1 hour.The precontacting step, the postcontacting step, or both, can increasethe productivity of the polymer as compared to the same catalystcomposition that is prepared without precontacting or postcontacting.However, neither a precontacting step nor a postcontacting step isrequired.

The postcontacted mixture can be heated at a temperature and for a timeperiod sufficient to allow adsorption, impregnation, or interaction ofprecontacted mixture and the activator-support, such that a portion ofthe components of the precontacted mixture can be immobilized, adsorbed,or deposited thereon. Where heating is employed, the postcontactedmixture generally can be heated to a temperature of from between about0° F. to about 150° F., or from about 40° F. to about 95° F.

According to one aspect of this invention, the weight percentage ofcatalyst component I can be in a range from about 5 to about 80%, theweight percentage of catalyst component II can be in a range from about5 to about 80%; and the weight percentage of catalyst component III canbe in a range from about 5 to about 80%. These weight percentages arebased on the total weight of catalyst components I, II, and III equaling100%, and does not include other components of the catalyst composition,e.g., activator, co-catalyst, etc. In another aspect, the catalystcomposition can contain from about 20 to about 50 wt. % catalystcomponent I, from about 5 to about 30 wt. % catalyst component II, andfrom about 20 to about 50 wt. % catalyst component III (as above, theweight percentage is based on the total weight of catalyst components I,II, and III equaling 100%). In yet another aspect, the catalystcomposition can contain from about 25 to about 45 wt. % catalystcomponent I, from about 5 to about 30 wt. % catalyst component II, andfrom about 25 to about 45 wt. % catalyst component III. In these andother aspects, the weight percentage of catalyst component II can be ina range from about 5 to about 25%, from about 5 to about 20%, or fromabout 10 to about 25%. Furthermore, the weight ratio of catalystcomponent I to catalyst component III, in some aspects, can be in arange from about 10:1 to about 1:10, from about 8:1 to about 1:8, fromabout 5:1 to about 1:5, from about 4:1 to about 1:4, from about 3:1 toabout 1:3; from about 2:1 to about 1:2, from about 1.5:1 to about 1:1.5,from about 1.25:1 to about 1:1.25, or from about 1.1:1 to about 1:1.1.

When a precontacting step is used, the molar ratio of the total moles ofolefin monomer to total moles of metallocene(s) in the precontactedmixture typically can be in a range from about 1:10 to about 100,000:1.Total moles of each component are used in this ratio to account foraspects of this invention where more than one olefin monomer and/or morethan one metallocene compound is employed in a precontacting step.Further, this molar ratio can be in a range from about 10:1 to about1,000:1 in another aspect of the invention.

Generally, the weight ratio of organoaluminum compound toactivator-support can be in a range from about 10:1 to about 1:1000. Ifmore than one organoaluminum compound and/or more than oneactivator-support is employed, this ratio is based on the total weightof each respective component. In another aspect, the weight ratio of theorganoaluminum compound to the activator-support can be in a range fromabout 3:1 to about 1:100, or from about 1:1 to about 1:50.

In some aspects of this invention, the weight ratio of metallocenecompounds (total of catalyst component I, II, and III) toactivator-support can be in a range from about 1:1 to about 1:1,000,000.If more than one activator-support is employed, this ratio is based onthe total weight of the activator-support. In another aspect, thisweight ratio can be in a range from about 1:5 to about 1:100,000, orfrom about 1:10 to about 1:10,000. Yet, in another aspect, the weightratio of the metallocene compounds to the activator-support can be in arange from about 1:20 to about 1:1000.

Catalyst compositions of the present invention generally have a catalystactivity greater than about 100 grams of polyethylene (homopolymer,copolymer, etc., as the context requires) per gram of activator-supportper hour (abbreviated g/g/hr). In another aspect, the catalyst activitycan be greater than about 150, greater than about 250, or greater thanabout 500 g/g/hr. In still another aspect, catalyst compositions of thisinvention can be characterized by having a catalyst activity greaterthan about 550, greater than about 650, or greater than about 750g/g/hr. Yet, in another aspect, the catalyst activity can be greaterthan about 1000 g/g/hr, greater than about 1500 g/g/hr, or greater thanabout 2000 g/g/hr. These activities are measured under slurrypolymerization conditions using isobutane as the diluent, at apolymerization temperature of about 95° C. and a reactor pressure ofabout 420 psig. Moreover, such catalyst activities can be achieved whenthe catalyst composition contains a co-catalyst, such as anorganoaluminum compound (e.g., triethylaluminum, triisobutylaluminum,etc.). Additionally, in some aspects, the activator-support can comprisesulfated alumina, fluorided silica-alumina, or fluorided silica-coatedalumina, although not limited thereto.

As discussed above, any combination of catalyst component I, catalystcomponent II, catalyst component III, the activator-support, theorganoaluminum compound, and the olefin monomer, can be precontacted insome aspects of this invention. When any precontacting occurs with anolefinic monomer, it is not necessary that the olefin monomer used inthe precontacting step be the same as the olefin to be polymerized.Further, when a precontacting step among any combination of the catalystcomponents is employed for a first period of time, this precontactedmixture can be used in a subsequent postcontacting step between anyother combination of catalyst components for a second period of time.For example, one or more metallocene compounds, the organoaluminumcompound, and 1-hexene can be used in a precontacting step for a firstperiod of time, and this precontacted mixture then can be contacted withthe activator-support to form a postcontacted mixture that can becontacted for a second period of time prior to initiating thepolymerization reaction. For example, the first period of time forcontact, the precontact time, between any combination of the metallocenecompound(s), the olefinic monomer, the activator-support, and theorganoaluminum compound can be from about 1 minute to about 24 hours,from about 3 minutes to about 1 hour, or from about 10 minutes to about30 minutes. The postcontacted mixture optionally can be allowed toremain in contact for a second period of time, the postcontact time,prior to initiating the polymerization process. According to one aspectof this invention, postcontact times between the precontacted mixtureand any remaining catalyst components can be from about 1 minute toabout 24 hours, or from about 5 minutes to about 1 hour.

Polymerization Processes

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like. Onesuch process for polymerizing olefins in the presence of a catalystcomposition of the present invention can comprise contacting thecatalyst composition with an olefin monomer and optionally an olefincomonomer (one or more) under polymerization conditions to produce anolefin polymer, wherein the catalyst composition can comprise catalystcomponent I, catalyst component II, catalyst component III, anactivator, and an optional co-catalyst. Catalyst components I, II, andIII are discussed above. For instance, catalyst component I can comprisean unbridged metallocene compound having formula (A), catalyst componentII can comprise a bridged metallocene compound having formula (B), andcatalyst component III can comprise a bridged metallocene compoundhaving formula (C).

In accordance with one aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising catalyst componentI, catalyst component II, catalyst component III, and an activator,wherein the activator comprises an activator-support. Activator-supportsuseful in the polymerization processes of the present invention aredisclosed above. The catalyst composition, optionally, can furthercomprise one or more than one organoaluminum compound or compounds (orother suitable co-catalyst). Thus, a process for polymerizing olefins inthe presence of a catalyst composition can employ a catalyst compositioncomprising catalyst component I, catalyst component II, catalystcomponent III, an activator-support, and an organoaluminum compound. Insome aspects, the activator-support can comprise (or consist essentiallyof, or consist of) fluorided alumina, chlorided alumina, bromidedalumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, and the like, or combinations thereof.In some aspects, the organoaluminum compound can comprise (or consistessentially of, or consist of) trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride,diethylaluminum ethoxide, diethylaluminum chloride, and the like, orcombinations thereof.

In accordance with another aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising catalyst componentI, catalyst component II, catalyst component III, an activator-support,and an optional co-catalyst, wherein the co-catalyst can comprise analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, an organoaluminum compound, an organozinccompound, an organomagnesium compound, or an organolithium compound, orany combination thereof. Hence, aspects of this invention are directedto a process for polymerizing olefins in the presence of a catalystcomposition, the processes comprising contacting a catalyst compositionwith an olefin monomer and optionally an olefin comonomer (one or more)under polymerization conditions to produce an olefin polymer, and thecatalyst composition can comprise catalyst component I, catalystcomponent II, catalyst component III, an activator-support, and analuminoxane compound; alternatively, catalyst component I, catalystcomponent II, catalyst component III, an activator-support, and anorganoboron or organoborate compound; alternatively, catalyst componentI, catalyst component II, catalyst component III, an activator-support,and an ionizing ionic compound; alternatively, catalyst component I,catalyst component II, catalyst component III, an activator-support, andan organoaluminum compound; alternatively, catalyst component I,catalyst component II, catalyst component III, an activator-support, andan organozinc compound; alternatively, catalyst component I, catalystcomponent II, catalyst component III, an activator-support, and anorganomagnesium compound; or alternatively, catalyst component I,catalyst component II, catalyst component III, an activator-support, andan organolithium compound. Furthermore, more than one co-catalyst can beemployed, e.g., an organoaluminum compound and an aluminoxane compound,an organoaluminum compound and an ionizing ionic compound, etc.

In accordance with another aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising only one catalystcomponent I metallocene compound, only one catalyst component IImetallocene compound, only one catalyst component III metallocenecompound, an activator-support, and an organoaluminum compound.

In accordance with another aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising catalyst componentI, catalyst component II, catalyst component III, and an activator,wherein the activator comprises an aluminoxane compound, an organoboronor organoborate compound, an ionizing ionic compound, or combinationsthereof.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactors. As used herein, “polymerization reactor” includes anypolymerization reactor capable of polymerizing olefin monomers andcomonomers (one or more than one comonomer) to produce homopolymers,copolymers, terpolymers, and the like. The various types of reactorsinclude those that can be referred to as a batch reactor, slurryreactor, gas-phase reactor, solution reactor, high pressure reactor,tubular reactor, autoclave reactor, and the like, or combinationsthereof. Suitable polymerization conditions are used for the variousreactor types. Gas phase reactors can comprise fluidized bed reactors orstaged horizontal reactors. Slurry reactors can comprise vertical orhorizontal loops. High pressure reactors can comprise autoclave ortubular reactors. Reactor types can include batch or continuousprocesses. Continuous processes could use intermittent or continuousproduct discharge. Processes can also include partial or full directrecycle of unreacted monomer, unreacted comonomer, and/or diluent.

Polymerization reactor systems of the present invention can comprise onetype of reactor in a system or multiple reactors of the same ordifferent type. Production of polymers in multiple reactors can includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorscan be different from the operating conditions of the other reactors.Alternatively, polymerization in multiple reactors can include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems can include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors canbe operated in series, in parallel, or both.

According to one aspect of the invention, the polymerization reactorsystem can comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and comonomer can becontinuously fed to a loop reactor where polymerization occurs.Generally, continuous processes can comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent can beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies can be used forthis separation step including but not limited to, flashing that caninclude any combination of heat addition and pressure reduction,separation by cyclonic action in either a cyclone or hydrocyclone, orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415,each of which is incorporated herein by reference in its entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under reaction conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used. An example is polymerization ofpropylene monomer as disclosed in U.S. Pat. No. 5,455,314, which isincorporated by reference herein in its entirety.

According to yet another aspect of this invention, the polymerizationreactor can comprise at least one gas phase reactor. Such systems canemploy a continuous recycle stream containing one or more monomerscontinuously cycled through a fluidized bed in the presence of thecatalyst under polymerization conditions. A recycle stream can bewithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product can be withdrawn from the reactor andnew or fresh monomer can be added to replace the polymerized monomer.Such gas phase reactors can comprise a process for multi-step gas-phasepolymerization of olefins, in which olefins are polymerized in thegaseous phase in at least two independent gas-phase polymerization zoneswhile feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another aspect of the invention, a high pressurepolymerization reactor can comprise a tubular reactor or an autoclavereactor. Tubular reactors can have several zones where fresh monomer,initiators, or catalysts are added. Monomer can be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components can be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamscan be intermixed for polymerization. Heat and pressure can be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor can comprise a solution polymerization reactor wherein themonomer/comonomer are contacted with the catalyst composition bysuitable stirring or other means. A carrier comprising an inert organicdiluent or excess monomer can be employed. If desired, themonomer/comonomer can be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation can be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactors suitable for the present invention can furthercomprise any combination of at least one raw material feed system, atleast one feed system for catalyst or catalyst components, and/or atleast one polymer recovery system. Suitable reactor systems for thepresent invention can further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Polymerization conditions that are controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. A suitable polymerization temperature canbe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from about 60°C. to about 280° C., for example, or from about 60° C. to about 120° C.,depending upon the type of polymerization reactor. In some reactorsystems, the polymerization temperature generally can fall within arange from about 70° C. to about 100° C., or from about 75° C. to about95° C.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). Pressure forgas phase polymerization is usually at about 200 to 500 psig (1.4 MPa to3.4 MPa). High pressure polymerization in tubular or autoclave reactorsis generally run at about 20,000 to 75,000 psig (138 to 517 MPa).Polymerization reactors can also be operated in a supercritical regionoccurring at generally higher temperatures and pressures. Operationabove the critical point of a pressure/temperature diagram(supercritical phase) may offer advantages.

Aspects of this invention are directed to olefin polymerizationprocesses comprising contacting a catalyst composition with an olefinmonomer and an olefin comonomer under polymerization conditions toproduce an olefin polymer. The olefin polymer (e.g., ethylene copolymer)produced by the process can have any of the polymer properties disclosedherein, for example, a melt index in a range from about 0.005 to about10 g/10 min, a ratio of HLMI/MI in a range from about 50 to about 500, adensity in a range from about 0.915 g/cm³ to about 0.965 g/cm³, and anon-bimodal molecular weight distribution.

Aspects of this invention also are directed to olefin polymerizationprocesses conducted in the absence of added hydrogen. An olefinpolymerization process of this invention can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer under polymerization conditions to produce an olefin polymer,wherein the catalyst composition can comprise catalyst component I,catalyst component II, catalyst component III, an activator, and anoptional co-catalyst, wherein the polymerization process is conducted inthe absence of added hydrogen. As one of ordinary skill in the art wouldrecognize, hydrogen can be generated in-situ by metallocene catalystcompositions in various olefin polymerization processes, and the amountgenerated can vary depending upon the specific catalyst composition andmetallocene compound(s) employed, the type of polymerization processused, the polymerization reaction conditions utilized, and so forth.

In other aspects, it may be desirable to conduct the polymerizationprocess in the presence of a certain amount of added hydrogen.Accordingly, an olefin polymerization process of this invention cancomprise contacting a catalyst composition with an olefin monomer andoptionally an olefin comonomer under polymerization conditions toproduce an olefin polymer, wherein the catalyst composition comprisescatalyst component I, catalyst component II, catalyst component III, anactivator, and an optional co-catalyst, wherein the polymerizationprocess is conducted in the presence of added hydrogen. For example, theratio of hydrogen to the olefin monomer in the polymerization processcan be controlled, often by the feed ratio of hydrogen to the olefinmonomer entering the reactor. The added hydrogen to olefin monomer ratioin the process can be controlled at a weight ratio which falls within arange from about 25 ppm to about 1500 ppm, from about 50 to about 1000ppm, or from about 100 ppm to about 750 ppm.

In some aspects of this invention, the feed or reactant ratio ofhydrogen to olefin monomer can be maintained substantially constantduring the polymerization run for a particular polymer grade. That is,the hydrogen:olefin monomer ratio can be selected at a particular ratiowithin a range from about 5 ppm up to about 1000 ppm or so, andmaintained at the ratio to within about +/−25% during the polymerizationrun. For instance, if the target ratio is 100 ppm, then maintaining thehydrogen:olefin monomer ratio substantially constant would entailmaintaining the feed ratio between about 75 ppm and about 125 ppm.Further, the addition of comonomer (or comonomers) can be, and generallyis, substantially constant throughout the polymerization run for aparticular polymer grade.

However, in other aspects, it is contemplated that monomer, comonomer(or comonomers), and/or hydrogen can be periodically pulsed to thereactor, for instance, in a manner similar to that employed in U.S. Pat.No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, thedisclosures of which are incorporated herein by reference in theirentirety.

The concentration of the reactants entering the polymerization reactorcan be controlled to produce resins with certain physical and mechanicalproperties. The proposed end-use product that will be formed by thepolymer resin and the method of forming that product ultimately candetermine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to, and encompasses, the polymersproduced by any of the polymerization processes disclosed herein.Articles of manufacture can be formed from, and/or can comprise, thepolymers produced in accordance with this invention.

Polymers and Articles

Olefin polymers encompassed herein can include any polymer produced fromany olefin monomer and comonomer(s) described herein. For example, theolefin polymer can comprise an ethylene copolymer (e.g.,ethylene/α-olefin, ethylene/1-butene, ethylene/1-hexene,ethylene/1-octene, etc.), a propylene copolymer, an ethylene terpolymer,a propylene terpolymer, and the like, including combinations thereof. Inone aspect, the olefin polymer can be an ethylene/1-butene copolymer, anethylene/1-hexene copolymer, or an ethylene/1-octene copolymer, while inanother aspect, the olefin polymer can be an ethylene/1-hexenecopolymer.

If the resultant polymer produced in accordance with the presentinvention is, for example, an ethylene polymer, its properties can becharacterized by various analytical techniques known and used in thepolyolefin industry. Articles of manufacture can be formed from, and/orcan comprise, the ethylene polymers of this invention, whose typicalproperties are provided below.

Polymers of ethylene (copolymers, terpolymers, etc.) produced inaccordance with some aspects of this invention generally can have a meltindex (MI) from about 0.005 to about 10 g/10 min. Melt indices in therange from 0.005 to about 5 g/10 min, from about 0.005 to about 2 g/10min, or from about 0.005 to about 1 g/10 min, are contemplated in otheraspects of this invention. For example, a polymer of the presentinvention can have a melt index in a range from about 0.01 to about 10,from about 0.01 to about 5, from about 0.01 to about 2, from about 0.01to about 1, from about 0.02 to about 1, from about 0.05 to about 2, orfrom about 0.05 to about 0.5 g/10 min.

Ethylene polymers produced in accordance with this invention can have aratio of HLMI/MI of greater than about 40, such as, for example, in arange from about 50 to about 500, from about 50 to about 400, or fromabout 50 to about 300. Other suitable ranges for HLMI/MI can include,but are not limited to, from about 60 to about 400, from about 60 toabout 250, from about 50 to about 200, from about 60 to about 200, fromabout 70 to about 200, or from about 50 to about 150, and the like.

The densities of ethylene-based polymers produced using the catalystsystems and processes disclosed herein often are greater than about 0.91g/cm³. In one aspect of this invention, the density of the ethylenepolymer can be in a range from about 0.915 to about 0.965 g/cm³. Yet, inanother aspect, the density can be in a range from about 0.92 to about0.96 g/cm³, such as, for example, from about 0.92 to about 0.95 g/cm³,from about 0.925 to about 0.955 g/cm³, or from about 0.93 to about 0.95g/cm³.

Ethylene polymers, such as copolymers, terpolymers, etc., consistentwith various aspects of the present invention generally can haveweight-average molecular weights (Mw's), for instance, in a range fromabout 150,000 to about 500,000 g/mol, from about 200,000 to about500,000 g/mol, from about 175,000 to about 400,000 g/mol, from about175,000 to about 350,000 g/mol, or from about 200,000 to about 300,000g/mol. Likewise, suitable non-limiting ranges of the number-averagemolecular weight (Mn) can include, but are not limited to, from about8,000 to about 30,000 g/mol, from about 8,000 to about 25,000 g/mol,from about 10,000 to about 25,000 g/mol, from about 10,000 to about18,000 g/mol, or from about 10,000 to about 15,000 g/mol. Moreover, thez-average molecular weight (Mz) of these polymers often can be greaterthan about 750,000 g/mol, and more often, greater than about 1,000,000g/mol. Contemplated Mz ranges encompassed by the present invention caninclude, but are not limited to, from about 750,000 to about 3,000,000g/mol, from about 750,000 to about 2,500,000 g/mol, from about 900,000to about 2,000,000 g/mol, from about 1,000,000 to about 3,000,000 g/mol,or from about 1,000,000 to about 2,000,000 g/mol.

The ratio of Mw/Mn, or the polydispersity index, for the polymers ofthis invention often can be in a range from about 10 to about 40. Insome aspects disclosed herein, the ratio of Mw/Mn can be in a range fromabout 10 to about 35, from about 10 to about 30, or from about 15 toabout 30. In other aspects, the ratio of Mw/Mn can be in a range fromabout 15 to about 40, from about 15 to about 35, or from about 15 toabout 25. The ratio of Mz/Mw for the polymers of this invention oftencan be in a range from about 3 to about 10. For example, the Mz/Mw ratiocan be in a range from about 3 to about 9, from about 3.5 to about 9,from about 4 to about 9, or from about 4 to about 8.

Ethylene-based polymers of this invention also can be characterized ashaving a non-bimodal molecular weight distribution. As used herein,“non-bimodal” means that there are not two distinguishable peaks in themolecular weight distribution curve (as determined using gel permeationchromatography (GPC) or other recognized analytical technique).Non-bimodal includes unimodal distributions, where there is only onepeak. Peaks also are not distinguishable if there are two peaks in themolecular weight distribution curve and there is no obvious valleybetween the peaks, or either one of the peaks is not considered as adistinguishable peak, or both peaks are not considered asdistinguishable peaks. FIGS. 1-5 illustrate representative bimodalmolecular weight distribution curves (amount of material versus thelogarithm of molecular weight). In these figures, there is a valleybetween the peaks, and the peaks can be separated or deconvoluted.Often, a bimodal molecular weight distribution is characterized ashaving an identifiable high molecular weight component (or distribution)and an identifiable low molecular weight component (or distribution). Incontrast, FIGS. 6-11 illustrate representative non-bimodal molecularweight distribution curves. These include unimodal molecular weightdistributions as well as distribution curves containing two peaks thatcannot be easily distinguished, separated, or deconvoluted.

Further, the ratio of the molecular weight of the polymer at D15 to themolecular weight of the polymer at D85 can be in a range from about 30to about 90. D85 is the molecular weight at which 85% of the polymer byweight has higher molecular weight, and D15 is the molecular weight atwhich 15% of the polymer by weight has higher molecular weight. D85 andD15 are depicted graphically in FIG. 12 for a molecular weightdistribution curve as a function of increasing logarithm of themolecular weight. In accordance with one aspect of the presentinvention, the ratio of the molecular weight of the polymer at D15 tothe molecular weight of the polymer at D85 can be in a range from about30 to about 85, or from about 40 to about 90. In another aspect, thisratio can be in a range from about 40 to about 85, from about 40 toabout 80, from about 40 to about 75, from about 40 to about 70, fromabout 35 to about 80, from about 35 to about 70, or from about 35 toabout 60.

Generally, polymers produced in aspects of the present invention havelow levels of long chain branching, with typically less than about 0.01long chain branches (LCB) per 1000 total carbon atoms, but greater thanzero. In some aspects, the number of LCB per 1000 total carbon atoms canbe less than about 0.008, less than about 0.007, less than about 0.005,or less than about 0.003 LCB per 1000 total carbon atoms.

Ethylene copolymers produced using the polymerization processes andcatalyst systems described above can, in some aspects, have a reversecomonomer distribution, i.e., a short chain branch content thatincreases as molecular weight increases, for example, the highermolecular weight components of the polymer generally have highercomonomer incorporation than the lower molecular weight components.Typically, there is increasing comonomer incorporation with increasingmolecular weight. For instance, the number of short chain branches (SCB)per 1000 total carbon atoms can be greater at Mw than at Mn. In anaspect, the ratio of the number of short chain branches (SCB) per 1000total carbon atoms of the polymer at Mw to the number of SCB per 1000total carbon atoms of the polymer at Mn can be a range from about 1.1:1to about 5:1, or alternatively, in a range from about 1.5:1 to about4:1.

The reverse short chain branching distribution (SCBD) or reversecomonomer distribution can be characterized by the average number ofshort chain branches (SCB) per 1000 total carbon atoms increasing foreach 10 wt. % fraction of polymer increasing from D85 to D15 (or fromD80 to D10, defined similarly to D85 and D15). In an aspect, forinstance, the average number of SCB per 1000 total carbon atoms in theD80 to D70 range is less than in the D70 to D60 range, which is lessthan in the D60 to D50 range, which is less than in the D50 to D40range, which is less than in the D40 to D30 range, which is less than inthe D30 to D20 O range, which is less than in the D20 to D10 range.

In another aspect, the SCBD of polymers of the present invention can becharacterized by the ratio of the number of SCB per 1000 total carbonatoms of the polymer at D10 to the number of SCB per 1000 total carbonatoms of the polymer at D50, i.e., (SCB at D10)/(SCB at D50). D50 is themolecular weight at which 50% of the polymer by weight has highermolecular weight, and D10 is the molecular weight at which 10% of thepolymer by weight has higher molecular weight. D50 and D10 are depictedgraphically in FIG. 13 for a molecular weight distribution curve as afunction of increasing logarithm of the molecular weight. In accordancewith one aspect of the present invention, a ratio of the number of SCBper 1000 total carbon atoms of the polymer at D10 to the number of SCBper 1000 total carbon atoms of the polymer at D50 can be in a range fromabout 1.1 to about 10. For instance, the ratio can be in a range fromabout 1.2 to about 10, from about 1.1 to about 5, from about 1.2 toabout 5, from about 1.5 to about 10, from about 2 to about 5, or fromabout 2 to about 4.

An illustrative and non-limiting example of an ethylene polymer of thepresent invention can be characterized by a melt index in a range fromabout 0.005 to about 10 g/10 min, a ratio of HLMI/MI in a range fromabout 50 to about 500, a density in a range from about 0.915 g/cm³ toabout 0.965 g/cm³, and a non-bimodal molecular weight distribution.Another illustrative and non-limiting example of an ethylene polymer ofthe present invention can be characterized by a melt index in a rangefrom about 0.01 to about 2 g/10 min, a ratio of HLMI/MI in a range fromabout 50 to about 200, a density in a range from about 0.925 g/cm³ toabout 0.955 g/cm³, and a non-bimodal (e.g., unimodal) molecular weightdistribution.

Polymers of ethylene, whether copolymers, terpolymers, and so forth, canbe formed into various articles of manufacture. Articles which cancomprise polymers of this invention include, but are not limited to, anagricultural film, an automobile part, a bottle, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, a toy,and the like. Various processes can be employed to form these articles.Non-limiting examples of these processes include injection molding, blowmolding, rotational molding, film extrusion, sheet extrusion, profileextrusion, thermoforming, and the like. Additionally, additives andmodifiers are often added to these polymers in order to providebeneficial polymer processing or end-use product attributes. Suchprocesses and materials are described in Modern Plastics Encyclopedia,Mid-November 1995 Issue, Vol. 72, No. 12; and Film ExtrusionManual—Process, Materials, Properties, TAPPI Press, 1992; thedisclosures of which are incorporated herein by reference in theirentirety.

Applicants also contemplate a method for forming or preparing an articleof manufacture comprising a polymer produced by any of thepolymerization processes disclosed herein. For instance, a method cancomprise (i) contacting a catalyst composition with an olefin monomerand an olefin comonomer (one or more) under polymerization conditions toproduce an olefin polymer, wherein the catalyst composition can comprisecatalyst component I, catalyst component II, catalyst component III, anactivator (e.g., an activator-support comprising a solid oxide treatedwith an electron-withdrawing anion), and an optional co-catalyst (e.g.,an organoaluminum compound); and (ii) forming an article of manufacturecomprising the olefin polymer. The forming step can comprise blending,melt processing, extruding, molding, or thermoforming, and the like,including combinations thereof.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight. High load melt index (HLMI, g/10min) was determined in accordance with ASTM D1238 at 190° C. with a21,600 gram weight.

Polymer density was determined in grams per cubic centimeter (g/cm³) ona compression molded sample, cooled at about 15° C. per hour, andconditioned for about 40 hours at room temperature in accordance withASTM D1505 and ASTM D1928, procedure C.

Molecular weights and molecular weight distributions were obtained usinga PL-GPC 220 (Polymer Labs, an Agilent Company) system equipped with aIR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns(Waters, Mass.) running at 145° C. The flow rate of the mobile phase1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymersolution concentrations were in the range of 1.0-1.5 mg/mL, depending onthe molecular weight. Sample preparation was conducted at 150° C. fornominally 4 hr with occasional and gentle agitation, before thesolutions were transferred to sample vials for injection. The integralcalibration method was used to deduce molecular weights and molecularweight distributions using a Chevron Phillips Chemicals Company's HDPEpolyethylene resin, MARLEX® BHB5003, as the broad standard. The integraltable of the broad standard was pre-determined in a separate experimentwith SEC-MALS.

Short chain branch content and short chain branching distribution (SCBD)across the molecular weight distribution were determined via anIR5-detected GPC system (IR5-GPC), wherein the GPC system was a PL220GPC/SEC system (Polymer Labs, an Agilent company) equipped with threeStyragel HMW-6E columns (Waters, Mass.) for polymer separation. Athermoelectric-cooled IR5 MCT detector (IR5) (Polymer Char, Spain) wasconnected to the GPC columns via a hot-transfer line. Chromatographicdata were obtained from two output ports of the IR5 detector. First, theanalog signal goes from the analog output port to a digitizer beforeconnecting to Computer “A” for molecular weight determinations via theCirrus software (Polymer Labs, now an Agilent Company) and the integralcalibration method using a broad MWD HDPE Marlex™ BHB5003 resin (ChevronPhillips Chemical) as the broad molecular weight standard. The digitalsignals, on the other hand, go via a USB cable directly to Computer “B”where they are collected by a LabView data collection software providedby Polymer Char. Chromatographic conditions were set as follows: columnoven temperature of 145° C.; flowrate of 1 mL/min; injection volume of0.4 mL; and polymer concentration of about 2 mg/mL, depending on samplemolecular weight. The temperatures for both the hot-transfer line andIR5 detector sample cell were set at 150° C., while the temperature ofthe electronics of the IR5 detector was set at 60° C. Short chainbranching content was determined via an in-house method using theintensity ratio of CH₃ (I_(CH3)) to CH₂ (I_(CH2)) coupled with acalibration curve. The calibration curve was a plot of SCB content(X_(SCB)) as a function of the intensity ratio of I_(CH3)/I_(CH2). Toobtain a calibration curve, a group of polyethylene resins (no less than5) of SCB level ranging from zero to ca. 32 SCB/1,000 total carbons (SCBStandards) were used. All these SCB Standards have known SCB levels andflat SCBD profiles pre-determined separately by NMR and thesolvent-gradient fractionation coupled with NMR (SGF-NMR) methods. UsingSCB calibration curves thus established, profiles of short chainbranching distribution across the molecular weight distribution wereobtained for resins fractionated by the IR5-GPC system under exactly thesame chromatographic conditions as for these SCB standards. Arelationship between the intensity ratio and the elution volume wasconverted into SCB distribution as a function of MWD using apredetermined SCB calibration curve (i.e., intensity ratio ofI_(CH3)/I_(CH2) vs. SCB content) and MW calibration curve (i.e.,molecular weight vs. elution time) to convert the intensity ratio ofI_(CH3)/I_(CH2) and the elution time into SCB content and the molecularweight, respectively.

Long chain branches (LCB) per 1000 total carbon atoms can be determinedas described in U.S. Pat. No. 8,114,946, “Diagnosing Long-ChainBranching in Polyethylenes,” J. Mol. Struct. 485-486, 569-584 (1999),and J. Phys. Chem. 1980, 84, 649, the disclosures of which areincorporated herein by reference in their entirety.

Sulfated alumina activator-supports were prepared as follows. Bohemitewas obtained from W.R. Grace & Company under the designation “Alumina A”and having a surface area of about 300 m²/g and a pore volume of about1.3 mL/g This material was obtained as a powder having an averageparticle size of about 100 microns. This material was impregnated toincipient wetness with an aqueous solution of ammonium sulfate to equalabout 15% sulfate. This mixture was then placed in a flat pan andallowed to dry under vacuum at approximately 110° C. for about 16 hours.To calcine the resultant powdered mixture, the material was fluidized ina stream of dry air at about 550° C. for about 6 hours. Afterward, thesulfated alumina was collected and stored under dry nitrogen, and wasused without exposure to the atmosphere.

Examples 1-6

Examples 1-4 were produced using the following polymerization procedure.All polymerization runs were conducted in a one-gallon stainless steelreactor. Isobutane (1.8 L) was used in all runs. Metallocene solutionswere prepared at about 1 mg/mL in toluene. Approximately 1 mmol of alkylaluminum (triisobutylaluminum), 300 mg of sulfated alumina, and themetallocene solutions were added in that order through a charge portwhile slowly venting isobutane vapor. The charge port was closed andisobutane was added. The contents of the reactor were stirred and heatedto the desired run temperature of about 95° C., and ethylene was thenintroduced into the reactor with 10 g of 1-hexene and hydrogen at 300ppm by weight of the ethylene. Ethylene and hydrogen were fed on demandat the specified weight ratio to maintain the target pressure of 420psig pressure for the 40-minute length of the polymerization run. Thereactor was maintained at the desired run temperature throughout the runby an automated heating-cooling system. The following metallocenecompounds were used in Examples 1-4:

Table I summarizes certain processing conditions and properties of thepolymers of Examples 1-6. Example 5 was an ethylene copolymer producedusing a chromium-based catalyst system (TR480), and Example 6 was anethylene copolymer produced using a chromium-based catalyst system(TR418).

In Table I, Mn is the number-average molecular weight, Mw is theweight-average molecular weight, Mz is the z-average molecular weight,MI in the melt index, and HLMI is the high load melt index. Table IIsummarizes the D10, D15, D50, D80, and D85 molecular weights for thepolymers of Examples 1-6, and Table III summarizes the number of shortchain branches per 1000 total carbon atoms at D10 and D50 for thepolymers of Examples 1-6. FIG. 14 illustrates the molecular weightdistributions of the polymers of Examples 1-6, and FIGS. 15-19illustrates the short chain branching distributions of the polymers ofExamples 1-6.

As shown in Tables I-II and FIG. 14, the polymers of Examples 1-4 hadbroad (and non-bimodal) molecular weight distributions (Mw/Mn's from 16to 21) with large melt flow ratios (HLMI/MI from 102 to 155). Thereverse comonomer distribution and increasing levels of SCB per 1000total carbon atoms for Examples 1-4 are illustrated in FIGS. 15-18 andTable III, and contrasted with the opposite SCB profile of Examples 5-6illustrated in FIG. 19 and Table III.

TABLE I Processing Conditions and Polymer Properties of Examples 1-6.MTE-1 MTE-2 MTE-3 Polymer Produced Example (mg) (mg) (mg) (g) 1 2.0 0.22.0 133 2 2.0 0.3 2.0 146 3 2.0 0.4 2.0 147 4 2.0 0.5 2.0 153 Mn/1000Mw/1000 Mz/1000 MI HLMI Density Example (kg/mol) (kg/mol) (kg/mol) Mw/Mn(g/10 min) (g/10 min) HLMI/MI (g/cc) 1 12.0 247.9 1278.1 20.7 0.08 9.9132 0.9468 2 12.8 246.4 1062.7 19.3 0.08 11.6 155 0.9444 3 13.0 247.31217.6 19.1 0.09 8.9 102 0.9438 4 14.2 237.5 1144.9 16.7 0.08 10.2 1220.9436 5 14.9 261.6 1850.6 17.6 0.11 9.0 82 0.9440 6 13.1 203.1 1513.115.5 0.21 19.4 92 0.9390

TABLE II Certain Molecular Weight Properties of the Polymers of Examples1-6. Molecular Weight (g/mol) Example D10 D15 D50 D80 D85 1 662,100484,800 66,800 13,200 8,700 2 722,200 497,100 73,300 14,600 9,600 3670,300 490,900 77,200 14,400 9,400 4 614,400 449,800 80,300 16,00010,500 5 612,200 427,700 83,200 19,200 12,600 6 455,200 311,500 55,50015,000 10,000

TABLE III Short Chain Branch Content of the Polymers of Examples 1-6.SCB/1000 C Example D10 D50 1 7.1 2.3 2 7.3 2.6 3 8.3 3.2 4 6.7 2.5 5 1.62.9 6 4.5 7.0

The invention has been described above with reference to numerousaspects and embodiments, and specific examples. Many variations willsuggest themselves to those skilled in the art in light of the abovedetailed description. All such obvious variations are within the fullintended scope of the appended claims. Other embodiments of theinvention can include, but are not limited to, the following:

Embodiment 1. An olefin polymer having a melt index in a range fromabout 0.005 to about 10 g/10 min, a ratio of HLMI/MI in a range fromabout 50 to about 500, a density in a range from about 0.915 g/cm³ toabout 0.965 g/cm³, and a non-bimodal molecular weight distribution.

Embodiment 2. The polymer defined in embodiment 1, wherein the olefinpolymer has a melt index in any range disclosed herein, e.g., from about0.01 to about 2, from about 0.01 to about 1, from about 0.02 to about 1,from about 0.05 to about 0.5 g/10 min, etc.

Embodiment 3. The polymer defined in any one of embodiments 1-2, whereinthe olefin polymer has a ratio of HLMI/MI in any range disclosed herein,e.g., from about 50 to about 300, from about 60 to about 250, from about50 to about 200, from about 70 to about 200, etc.

Embodiment 4. The polymer defined in any one of embodiments 1-3, whereinthe olefin polymer has a density in any range disclosed herein, e.g.,from about 0.92 to about 0.96, from about 0.925 to about 0.955, fromabout 0.93 to about 0.95 g/cm³, etc.

Embodiment 5. The polymer defined in any one of embodiments 1-4, whereinthe olefin polymer has a unimodal molecular weight distribution.

Embodiment 6. The polymer defined in any one of embodiments 1-5, whereinthe olefin polymer has a ratio of Mw/Mn in any range disclosed herein,e.g., from about 10 to about 40, from about 15 to about 35, from about15 to about 30, from about 15 to about 25, etc.

Embodiment 7. The polymer defined in any one of embodiments 1-6, whereinthe olefin polymer has a ratio of Mz/Mw in any range disclosed herein,e.g., from about 3 to about 10, from about 3.5 to about 9, from about 4to about 9, from about 4 to about 8, etc.

Embodiment 8. The polymer defined in any one of embodiments 1-7, whereinthe olefin polymer has a Mw in any range disclosed herein, e.g., fromabout 150,000 to about 500,000, from about 200,000 to about 500,000,from about 175,000 to about 400,000, from about 200,000 to about 300,000g/mol, etc.

Embodiment 9. The polymer defined in any one of embodiments 1-8, whereinthe olefin polymer has a Mn in any range disclosed herein, e.g., fromabout 8,000 to about 30,000, from about 10,000 to about 25,000, fromabout 10,000 to about 18,000, from about 10,000 to about 15,000 g/mol,etc.

Embodiment 10. The polymer defined in any one of embodiments 1-9,wherein the olefin polymer has a Mz is any range disclosed herein, e.g.,from about 750,000 to about 2,500,000, from about 900,000 to about2,000,000, from about 1,000,000 to about 2,000,000 g/mol, etc.

Embodiment 11. The polymer defined in any one of embodiments 1-10,wherein a ratio of the molecular weight of the polymer at D15 to themolecular weight of the polymer at D85 is in any range disclosed herein,e.g., from about 30 to about 90, from about 40 to about 80, from about40 to about 70, etc.

Embodiment 12. The polymer defined in any one of embodiments 1-11,wherein the olefin polymer has less than about 0.008 long chain branches(LCB) per 1000 total carbon atoms, e.g., less than about 0.005 LCB, lessthan about 0.003 LCB, etc.

Embodiment 13. The polymer defined in any one of embodiments 1-12,wherein the olefin polymer has a reverse comonomer distribution, e.g.,the average number of short chain branches (SCB) per 1000 total carbonatoms increases for each 10 wt. % fraction of polymer increasing fromD80 to D10 (or from D85 to D15), the number of SCB per 1000 total carbonatoms of the polymer at Mw is greater than at Mn, etc.

Embodiment 14. The polymer defined in any one of embodiments 1-13,wherein a ratio of the number of short chain branches (SCB) per 1000total carbon atoms of the polymer at D10 to the number of SCB per 1000total carbon atoms of the polymer at D50 is in any range disclosedherein, e.g., from about 1.1 to about 10, from about 1.2 to about 5,from about 2 to about 5, etc.

Embodiment 15. The polymer defined in any one of embodiments 1-14,wherein the olefin polymer is an ethylene/1-butene copolymer, anethylene/1-hexene copolymer, or an ethylene/1-octene copolymer.

Embodiment 16. The polymer defined in any one of embodiments 1-15,wherein the olefin polymer is an ethylene/1-hexene copolymer.

Embodiment 17. An article comprising the olefin polymer defined in anyone of embodiments 1-16.

Embodiment 18. An article comprising the olefin polymer defined in anyone of embodiments 1-16, wherein the article is an agricultural film, anautomobile part, a bottle, a drum, a fiber or fabric, a food packagingfilm or container, a food service article, a fuel tank, a geomembrane, ahousehold container, a liner, a molded product, a medical device ormaterial, a pipe, a sheet or tape, or a toy.

Embodiment 19. A catalyst composition comprising catalyst component I,catalyst component II, catalyst component III, an activator, and anoptional co-catalyst, wherein catalyst component I comprises anunbridged zirconium or hafnium based metallocene compound and/or anunbridged zirconium and/or hafnium based dinuclear metallocene compound;catalyst component II comprises a bridged zirconium based metallocenecompound with a fluorenyl group, and with no aryl groups on the bridginggroup; and catalyst component III comprises a bridged zirconium orhafnium based metallocene compound with a fluorenyl group, and an arylgroup on the bridging group.

Embodiment 20. The composition defined in embodiment 19, wherein theactivator comprises any activator disclosed herein.

Embodiment 21. The composition defined in any one of embodiments 19-20,wherein the activator comprises an aluminoxane compound, an organoboronor organoborate compound, an ionizing ionic compound, or any combinationthereof.

Embodiment 22. The composition defined in any one of embodiments 19-20,wherein the activator comprises an activator-support, theactivator-support comprising any solid oxide treated with anyelectron-withdrawing anion disclosed herein.

Embodiment 23. The composition defined in embodiment 22, wherein theactivator-support comprises any activator-support disclosed herein,e.g., fluorided alumina, sulfated alumina, fluorided silica-alumina,sulfated silica-alumina, fluorided silica-coated alumina, sulfatedsilica-coated alumina, phosphated silica-coated alumina, etc., or anycombination thereof

Embodiment 24. The composition defined in any one of embodiments 19-23,wherein the co-catalyst comprises any co-catalyst disclosed herein.

Embodiment 25. The composition defined in any one of embodiments 19-24,wherein the co-catalyst comprises an organoaluminum compound, anorganozinc compound, an organomagnesium compound, an organolithiumcompound, or any combination thereof.

Embodiment 26. The composition defined in any one of embodiments 19-20,wherein the catalyst composition comprises catalyst component I,catalyst component II, catalyst component III, a solid oxide treatedwith an electron-withdrawing anion, and an organoaluminum compound.

Embodiment 27. The composition defined in embodiment 26, wherein theorganoaluminum compound comprises any organoaluminum compound disclosedherein, e.g., trimethylaluminum, triethylaluminum, triisobutylaluminum,etc., or combinations thereof.

Embodiment 28. The composition defined in any one of embodiments 26-27,wherein the solid oxide treated with an electron-withdrawing anioncomprises any solid oxide treated with an electron-withdrawing aniondisclosed herein, e.g., fluorided alumina, sulfated alumina, fluoridedsilica-alumina, sulfated silica-alumina, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, etc., or any combination thereof.

Embodiment 29. The composition defined in any one of embodiments 22-28,wherein the co-catalyst comprises an aluminoxane compound, anorganoboron or organoborate compound, an ionizing ionic compound, anorganoaluminum compound, an organozinc compound, an organomagnesiumcompound, an organolithium compound, or any combination thereof.

Embodiment 30. The composition defined in any one of embodiments 22-28,wherein the catalyst composition is substantially free of aluminoxanecompounds, organoboron or organoborate compounds, ionizing ioniccompounds, or combinations thereof.

Embodiment 31. The composition defined in any one of embodiments 19-30,wherein the catalyst composition comprises only one unbridged zirconiumor hafnium based metallocene compound or unbridged zirconium and/orhafnium based dinuclear metallocene compound; only one bridged zirconiumbased metallocene compound with a fluorenyl group, and with no arylgroups on the bridging group; and only one bridged zirconium or hafniumbased metallocene compound with a fluorenyl group, and an aryl group onthe bridging group.

Embodiment 32. The composition defined in any one of embodiments 19-31,wherein catalyst component I comprises an unbridged zirconium or hafniumbased metallocene compound containing two cyclopentadienyl groups, twoindenyl groups, or a cyclopentadienyl and an indenyl group.

Embodiment 33. The composition defined in any one of embodiments 19-31,wherein catalyst component I comprises an unbridged zirconium basedmetallocene compound containing two cyclopentadienyl groups, two indenylgroups, or a cyclopentadienyl and an indenyl group.

Embodiment 34. The composition defined in any one of embodiments 19-31,wherein catalyst component I comprises an unbridged zirconium basedhomodinuclear metallocene compound.

Embodiment 35. The composition defined in any one of embodiments 19-31,wherein catalyst component I comprises an unbridged hafnium basedhomodinuclear metallocene compound.

Embodiment 36. The composition defined in any one of embodiments 19-31,wherein catalyst component I comprises an unbridged zirconium and/orhafnium based heterodinuclear metallocene compound.

Embodiment 37. The composition defined in any one of embodiments 19-31,wherein catalyst component I comprises any unbridged metallocenecompound or unbridged dinuclear metallocene compound disclosed herein,e.g., having formula (A):

wherein M¹ is Zr or Hf; Cp^(A) and Cp^(B) independently are asubstituted or unsubstituted cyclopentadienyl or indenyl group; and eachX independently is a monoanionic ligand.

Embodiment 38. The composition defined in embodiment 37, wherein M¹ isZr.

Embodiment 39. The composition defined in any one of embodiments 37-38,wherein Cp^(A) and Cp^(B) independently are a substituted indenyl orcyclopentadienyl group with any number of substituents disclosed herein,e.g., one substituent, two substituents, etc.

Embodiment 40. The composition defined in embodiment 37, wherein Cp^(A)and Cp^(B) independently are an unsubstituted cyclopentadienyl orindenyl group.

Embodiment 41. The composition defined in any one of embodiments 19-40,wherein catalyst component II comprises a bridged zirconium basedmetallocene compound with a cyclopentadienyl group and a fluorenylgroup, and with no aryl groups on the bridging group.

Embodiment 42. The composition defined in any one of embodiments 19-41,wherein catalyst component II comprises any bridged zirconium basedmetallocene compound with a fluorenyl group, and with no aryl groups onthe bridging group, disclosed herein, e.g., having formula (B):

wherein Cp^(C) is a substituted cyclopentadienyl, indenyl, or fluorenylgroup; each X independently is a monoanionic ligand; R^(X) and R^(Y)independently are H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ toC₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or aC₁ to C₃₆ hydrocarbylsilyl group; and E² is a bridging group selectedfrom a bridging group having the formula >E^(A)R^(A)R^(B), wherein E^(A)is C, Si, or Ge, and R^(A) and R^(B) independently are H or a C₁ to C₁₈hydrocarbyl group, a bridging group having the formula—CR^(C)R^(D)—CR^(E)R^(E)—, wherein R^(C), R^(D), R^(E), and R^(E)independently are H or a C₁ to C₁₈ hydrocarbyl group, or a bridginggroup having the formula —SiR^(G)R^(H)-E⁵R^(I)R^(J)—, wherein E⁵ is C orSi, and R^(G), R^(H), R^(I), and R^(J) independently are H or a C₁ toC₁₈, hydrocarbyl group, and wherein R^(A), R^(B), R^(C), R^(D), R^(E),R^(F), R^(G), R^(H), R^(I), and R^(J) are not aryl groups.

Embodiment 43. The composition defined in embodiment 42, wherein Cp^(C)is a substituted cyclopentadienyl group with any number of substituentsdisclosed herein, e.g., one substituent, two substituents, etc., inaddition to the bridging group.

Embodiment 44. The composition defined in embodiment 42, wherein Cp^(C)contains no additional substituents, e.g., other than the bridginggroup.

Embodiment 45. The composition defined in any one of embodiments 42-44,wherein E² is a bridging group having the formula >E^(A)R^(A)R^(B),wherein E^(A) is C, Si, or Ge, and R^(A) and R^(B) independently are aC₁ to C₈ alkyl group or a C₃ to C₈ alkenyl group.

Embodiment 46. The composition defined in any one of embodiments 42-44,wherein E² is a bridging group having the formula >E^(A)R^(A)R^(B),wherein E^(A) is C, Si, or Ge, and R^(A) and R^(B) independently are amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, adecyl group, an ethenyl group, a propenyl group, a butenyl group, apentenyl group, a hexenyl group, a heptenyl group, an octenyl group, anonenyl group, or a decenyl group.

Embodiment 47. The composition defined in any one of embodiments 42-44,wherein E² is a bridging group having the formula—CR^(C)R^(D)—CR^(E)R^(F)—, wherein R^(C), R^(D), R^(E), and R^(E)independently are H or a methyl group.

Embodiment 48. The composition defined in any one of embodiments 42-44,wherein E² is a bridging group having the formula—SiR^(G)R^(H)-E⁵R^(I)R^(J)—, wherein E⁵ is Si, and R^(G), R^(H), R^(I),and R^(J) independently are H or a methyl group.

Embodiment 49. The composition defined in any one of embodiments 19-48,wherein catalyst component III comprises a bridged zirconium or hafniumbased metallocene compound with a cyclopentadienyl group and fluorenylgroup, and an aryl group on the bridging group.

Embodiment 50. The composition defined in any one of embodiments 19-48,wherein catalyst component III comprises a bridged zirconium basedmetallocene compound with a fluorenyl group, and an aryl group on thebridging group.

Embodiment 51. The composition defined in any one of embodiments 19-48,wherein catalyst component III comprises a bridged hafnium basedmetallocene compound with a fluorenyl group, and an aryl group on thebridging group.

Embodiment 52. The composition defined in any one of embodiments 49-51,wherein the aryl group is a phenyl group.

Embodiment 53. The composition defined in any one of embodiments 19-48,wherein catalyst component III comprises any bridged metallocenecompound with an aryl group on the bridging group disclosed herein,e.g., having formula (C):

wherein M³ is Zr or Hf; Cp^(C) is a substituted cyclopentadienyl,indenyl, or fluorenyl group; each X independently is a monoanionicligand; R^(X) and R^(Y) independently are H, a halide, a C₁ to C₃₆hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group; E³ is C,Si, or Ge; and each R³ independently is H or a C₁ to C₁₈ hydrocarbylgroup, wherein at least one R³ is an aryl group having up to 18 carbonatoms.

Embodiment 54. The composition defined in embodiment 53, wherein M³ isZr.

Embodiment 55. The composition defined in embodiment 53, wherein M³ isHE

Embodiment 56. The composition defined in any one of embodiments 53-55,wherein Cp^(C) is a substituted cyclopentadienyl group with any numberof substituents disclosed herein, e.g., one substituent, twosubstituents, etc., in addition to the bridging group.

Embodiment 57. The composition defined in any one of embodiments 53-55,wherein Cp^(C) contains no additional substituents, e.g., other than thebridging group.

Embodiment 58. The composition defined in any one of embodiments 53-57,wherein E³ is C.

Embodiment 59. The composition defined in any one of embodiments 53-58,wherein one R³ is a phenyl group and the other R³ is a C₁ to C₈ alkylgroup or a C₃ to C₈ alkenyl group.

Embodiment 60. The composition defined in any one of embodiments 53-59,wherein each R³ independently is a methyl group, an ethyl group, apropyl group, a butyl group, a pentyl group, a hexyl group, a heptylgroup, an octyl group, a nonyl group, a decyl group, an ethenyl group, apropenyl group, a butenyl group, a pentenyl group, a hexenyl group, aheptenyl group, an octenyl group, a nonenyl group, a decenyl group, aphenyl group, a cyclohexylphenyl group, a naphthyl group, a tolyl group,or a benzyl group, wherein at least one R³ is a phenyl group.

Embodiment 61. The composition defined in any one of embodiments 53-60,wherein each R³ is a phenyl group.

Embodiment 62. The composition defined in any one of embodiments 37-40,42-48, and 53-61, wherein each X independently is any monoanionic liganddisclosed herein.

Embodiment 63. The composition defined in any one of embodiments 37-40,42-48, and 53-61, wherein each X independently is H, BH₄, a halide, a C₁to C₃₆ hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, a C₁ to C₃₆hydrocarbylaminyl group, a C₁ to C₃₆ hydrocarbylsilyl group, a C₁ to C₃₆hydrocarbylaminylsilyl group, OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ toC₃₆ hydrocarbyl group.

Embodiment 64. The composition defined in any one of embodiments 37-40,42-48, and 53-61, wherein each X independently is any halide or C₁ toC₁₈ hydrocarbyl group disclosed herein.

Embodiment 65. The composition defined in any one of embodiments 37-40,42-48, and 53-61, wherein each X is Cl.

Embodiment 66. The composition defined in any one of embodiments 37-39,42-43, 45-48, 53-56, and 58-65, wherein each substituent on Cp^(A),Cp^(B), and Cp^(C) independently is any substituent disclosed herein,e.g., H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁to C₃₆ hydrocarbylsilyl group.

Embodiment 67. The composition defined in any one of embodiments 37-39,42-43, 45-48, 53-56, and 58-65, wherein each substituent on Cp^(A),Cp^(B), and Cp^(C) independently is any C₁ to C₁₂ hydrocarbyl group orC₁ to C₁₂ hydrocarbylsilyl group disclosed herein.

Embodiment 68. The composition defined in any one of embodiments 37-39,42-43, 45-48, 53-56, and 58-65, wherein each substituent on Cp^(A),Cp^(B), and Cp^(C) independently is H, Cl, CF₃, a methyl group, an ethylgroup, a propyl group, a butyl group, a pentyl group, a hexyl group, aheptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a tolyl group, a benzyl group, a naphthyl group,a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilylgroup, or an allyldimethylsilyl group.

Embodiment 69. The composition defined in any one of embodiments 37-39,42-43, 45-48, 53-56, and 58-65, wherein each substituent on Cp^(A),Cp^(B), and Cp^(C) independently is a C₁ to C₈ alkyl group or a C₃ to C₈alkenyl group.

Embodiment 70. The composition defined in any one of embodiments 42-48and 53-69, wherein each R^(X) and R^(Y) independently is H or any C₁ toC₁₂ hydrocarbyl group disclosed herein.

Embodiment 71. The composition defined in any one of embodiments 42-48and 53-69, wherein each R^(X) and R^(Y) independently is H, a methylgroup, an ethyl group, a propyl group, a butyl group, a pentyl group, ahexyl group, a heptyl group, an octyl group, a nonyl group, a decylgroup, an ethenyl group, a propenyl group, a butenyl group, a pentenylgroup, a hexenyl group, a heptenyl group, an octenyl group, a nonenylgroup, a decenyl group, a phenyl group, a tolyl group, or a benzylgroup.

Embodiment 72. The composition defined in any one of embodiments 19-71,wherein the weight percentages of catalyst component I, catalystcomponent II, and catalyst component III are in any range of weightpercentages disclosed herein, e.g., the weight percentage of catalystcomponent I is in a range from about 5 to about 80%, the weightpercentage of catalyst component II is in a range from about 5 to about80%, and the weight percentage of catalyst component III is in a rangefrom about 5 to about 80%, wherein the weight percentages are based onthe total weight of catalyst components I, II, and III.

Embodiment 73. The composition defined in any one of embodiments 19-72,wherein the weight percentage of catalyst component I is in a range fromabout 20 to about 50%, the weight percentage of catalyst component II isin a range from about 5 to about 60%, and the weight percentage ofcatalyst component III is in a range from about 20 to about 45%, whereinthe weight percentages are based on the total weight of catalystcomponents I, II, and III.

Embodiment 74. The composition defined in any one of embodiments 19-73,wherein the weight percentage of catalyst component II is in a rangefrom about 5 to about 20%, based on the total weight of catalystcomponents I, II, and III.

Embodiment 75. The composition defined in any one of embodiments 19-74,wherein a weight ratio of catalyst component Ito catalyst component IIIin the catalyst composition is in any range of weight ratios disclosedherein, e.g., from about 1:10 to about 10:1, from about 3:1 to about1:3, from about 1.5:1 to about 1:1.5, etc.

Embodiment 76. An olefin polymerization process, the process comprisingcontacting the catalyst composition defined in any one of embodiments19-75 with an olefin monomer and an olefin comonomer underpolymerization conditions to produce an olefin polymer.

Embodiment 77. The process defined in embodiment 76, wherein the processis conducted in a batch reactor, a slurry reactor, a gas-phase reactor,a solution reactor, a high pressure reactor, a tubular reactor, anautoclave reactor, or a combination thereof.

Embodiment 78. The process defined in any one of embodiments 76-77,wherein the process is conducted in a slurry reactor, a gas-phasereactor, a solution reactor, or a combination thereof.

Embodiment 79. The process defined in any one of embodiments 76-78,wherein the process is conducted in a single reactor, e.g., a slurryreactor.

Embodiment 80. The process defined in any one of embodiments 76-79,wherein the process is conducted in two or more reactors.

Embodiment 81. The process defined in any one of embodiments 76-80,wherein the olefin monomer comprises any olefin monomer disclosedherein, e.g., a C₂-C₂₀ olefin.

Embodiment 82. The process defined in any one of embodiments 76-81,wherein the olefin monomer comprises ethylene or propylene.

Embodiment 83. The process defined in any one of embodiments 76-82,wherein the olefin monomer comprises ethylene and the olefin comonomercomprises a C₃-C₁₀ alpha-olefin.

Embodiment 84. The process defined in any one of embodiments 76-82,wherein the olefin monomer comprises ethylene, and the olefin comonomercomprises propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene,1-decene, styrene, or a mixture thereof.

Embodiment 85. The process defined in any one of embodiments 76-82,wherein the olefin monomer comprises ethylene, and the olefin comonomercomprises 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Embodiment 86. The process defined in any one of embodiments 76-85,wherein the olefin polymer comprises any olefin polymer disclosedherein.

Embodiment 87. The process defined in any one of embodiments 76-86,wherein the olefin polymer comprises an ethylene/1-butene copolymer, anethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or acombination thereof.

Embodiment 88. An olefin polymer produced by the olefin polymerizationprocess defined in any one of embodiments 76-87.

Embodiment 89. An olefin polymer of any one of claims 1-16 produced bythe olefin polymerization process of any one of claims 76-87.

Embodiment 90. An article comprising the olefin polymer defined in anyone of embodiments 88-89.

Embodiment 91. A method or forming or preparing an article ofmanufacture comprising an olefin polymer, the method comprising (i)performing the olefin polymerization process defined in any one ofembodiments 76-87 to produce the olefin polymer of any one of claims1-16, and (ii) forming the article of manufacture comprising the olefinpolymer, e.g., via any technique disclosed herein.

Embodiment 92. The article defined in any one of embodiments 90-91,wherein the article is an agricultural film, an automobile part, abottle, a drum, a fiber or fabric, a food packaging film or container, afood service article, a fuel tank, a geomembrane, a household container,a liner, a molded product, a medical device or material, a pipe, a sheetor tape, or a toy.

1. An olefin polymerization process, the process comprising: contactinga catalyst composition with an olefin monomer and an olefin comonomerunder polymerization conditions to produce an olefin polymer, whereinthe catalyst composition comprises catalyst component I, catalystcomponent II, catalyst component III, an activator, and an optionalco-catalyst, wherein: catalyst component I comprises an unbridgedzirconium or hafnium based metallocene compound and/or an unbridgedzirconium and/or hafnium based dinuclear metallocene compound; catalystcomponent II comprises a bridged zirconium based metallocene compoundwith a fluorenyl group, and with no aryl groups on the bridging group;and catalyst component III comprises a bridged zirconium or hafniumbased metallocene compound with a fluorenyl group, and an aryl group onthe bridging group.
 2. The process of claim 1, wherein the catalystcomposition comprises: an unbridged zirconium based metallocene compoundcontaining two cyclopentadienyl groups, two indenyl groups, or acyclopentadienyl and an indenyl group; a bridged zirconium basedmetallocene compound with a cyclopentadienyl group and a fluorenylgroup, and with no aryl groups on the bridging group; a bridgedzirconium or hafnium based metallocene compound with a cyclopentadienylgroup and fluorenyl group, and a phenyl group on the bridging group; anactivator-support comprising a solid oxide treated with anelectron-withdrawing anion; and an organoaluminum compound.
 3. Theprocess of claim 2, wherein the organoaluminum compound comprisestrimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, or any combination thereof.
 4. Theprocess of claim 2, wherein the activator-support comprises fluoridedalumina, chlorided alumina, bromided alumina, sulfated alumina,fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, or any combination thereof.
 5. The process of claim 1, whereincatalyst component I comprises an unbridged metallocene compound havingformula (A):

wherein: M¹ is Zr or Hf; Cp^(A) and Cp^(B) independently are asubstituted or unsubstituted cyclopentadienyl or indenyl group; and eachX independently is a monoanionic ligand.
 6. The process of claim 1,wherein catalyst component II comprises a bridged metallocene compoundhaving formula (B):

wherein: Cp^(C) is a substituted cyclopentadienyl, indenyl, or fluorenylgroup; each X independently is a monoanionic ligand; R^(X) and R^(Y)independently are H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ toC₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or aC₁ to C₃₆ hydrocarbylsilyl group; and E² is a bridging group selectedfrom: a bridging group having the formula >E^(A)R^(A)R^(B), whereinE^(A) is C, Si, or Ge, and R^(A) and R^(B) independently are H or a C₁to C₁₈ hydrocarbyl group, a bridging group having the formula—CR^(C)R^(D)—CR^(E)R^(F)—, wherein R^(C), R^(D), R^(E), and R^(E)independently are H or a C₁ to C₁₈ hydrocarbyl group, or a bridginggroup having the formula —SiR^(G)R^(H)-E⁵R^(I)R^(J)—, wherein E⁵ is C orSi, and R^(G), R^(H), R^(I), and R^(J) independently are H or a C₁ toC₁₈ hydrocarbyl group, wherein R^(A), R^(B), R^(C), R^(D), R^(E), R^(F),R^(G), R^(H), R^(I), and R^(J) are not aryl groups.
 7. The process ofclaim 1, wherein catalyst component III comprises a bridged metallocenecompound having formula (C):

wherein: M³ is Zr or Hf; Cp^(C) is a substituted cyclopentadienyl,indenyl, or fluorenyl group; each X independently is a monoanionicligand; R^(X) and R^(Y) independently are H, a halide, a C₁ to C₃₆hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group; E³ is C,Si, or Ge; and each R³ independently is H or a C₁ to C₁₈ hydrocarbylgroup, wherein at least one R³ is an aryl group having up to 18 carbonatoms.
 8. The process of claim 1, wherein the activator comprises analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, or any combination thereof.
 9. The process ofclaim 1, wherein the activator comprises an activator-support, theactivator-support comprising a solid oxide treated with anelectron-withdrawing anion.
 10. The process of claim 1, wherein theco-catalyst comprises an organoaluminum compound, an organozinccompound, an organomagnesium compound, an organolithium compound, or anycombination thereof.
 11. The process of claim 1, wherein the process isconducted in a batch reactor, slurry reactor, gas-phase reactor,solution reactor, high pressure reactor, tubular reactor, autoclavereactor, or a combination thereof.
 12. The process of claim 1, whereinthe olefin monomer comprises ethylene, and the olefin comonomercomprises 1-butene, 1-hexene, 1-octene, or a mixture thereof.
 13. Theprocess of claim 1, wherein the olefin polymer has: a melt index in arange from about 0.005 to about 10 g/10 min; a ratio of HLMI/MI in arange from about 50 to about 500; a density in a range from about 0.915g/cm³ to about 0.965 g/cm³; a non-bimodal molecular weight distribution;and a ratio of Mw/Mn in a range from about 10 about
 40. 14. A catalystcomposition comprising: catalyst component I comprising an unbridgedzirconium or hafnium based metallocene compound and/or an unbridgedzirconium and/or hafnium based dinuclear metallocene compound; catalystcomponent II comprising a bridged zirconium based metallocene compoundwith a fluorenyl group, and with no aryl groups on the bridging group;catalyst component III comprising a bridged zirconium or hafnium basedmetallocene compound with a fluorenyl group, and an aryl group on thebridging group; an activator; and optionally, a co-catalyst.
 15. Thecomposition of claim 14, wherein: a weight percentage of catalystcomponent I is in a range from about 20 to about 50%; a weightpercentage of catalyst component II is in a range from about 5 to about30%; and a weight percentage of catalyst component III is in a rangefrom about 20 to about 50%; wherein the weight percentages are based onthe total weight of catalyst components I, II, and III.
 16. An olefinpolymer having a melt index in a range from about 0.005 to about 10 g/10min, a ratio of HLMI/MI in a range from about 50 to about 500, a densityin a range from about 0.915 g/cm³ to about 0.965 g/cm³, and anon-bimodal molecular weight distribution.
 17. The polymer of claim 16,wherein: a ratio of Mw/Mn of the polymer is in a range from about 10about 40; and a ratio of the molecular weight of the polymer at D15 tothe molecular weight of the polymer at D85 is in a range from about 30to about
 90. 18. The polymer of claim 17, wherein the polymer has: areverse comonomer distribution; and a unimodal molecular weightdistribution.
 19. The polymer of claim 17, wherein: the melt index is ina range from about 0.01 to about 2 g/10 min; the ratio of HLMI/MI is ina range from about 50 to about 200; the density is in a range from about0.925 g/cm³ to about 0.955 g/cm³; the ratio of Mw/Mn is in a range fromabout 15 about 30; and the ratio of the molecular weight of the polymerat D15 to the molecular weight of the polymer at D85 is in a range fromabout 40 to about
 70. 20. An article comprising the polymer of claim 16.